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Inspector Knowledge Series 04-B


Effect of steel Alloying Elements



材料基础-钢材合金元素 图文简易教材


Descriptive approach





This Ebook are meant to be read with internet connection hook-on.
Online interactive material, videos and animations will assist you in the understanding of
corrosion basic. Video contents are highlighted by icons



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REVISION HISTORY






01 01.10.2008 For Approval Charlie C. CM Mok
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CHANGE DESCRIPTION

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Page 1 of 180.

Chapter One:
Theory of Strengthening

ƒ The Mechanism of Strengthening.
ƒ Elastic and Plastic Deformation.
ƒ Slide show on plastic deformation: Mechanical Testing
ƒ Understanding Dislocation.
ƒ The Nature of Dislocation.
ƒ "Atomistic" of edge and screw dislocation motions.
ƒ Origins of Strength from Dislocation Dynamics.
ƒ Deformation and strengthening Mechanisms.
ƒ Crystal Defects.
ƒ Point Defects
ƒ Linear Defects
ƒ Planar Defects.
ƒ Bulk Defects.
ƒ Pinning Overview.
ƒ Methods of Strengthening.
ƒ Works or Strain Hardening.
ƒ Strain Hardening and Annealing
ƒ Dislocation and plastic deformation
ƒ Grain Boundary Strengthening.
ƒ Effect of Microstructure Refinement on the Strength and Toughness of low alloy
martensitic steel
ƒ Effect of microstructure and notches on the fracture toughness of medium CS
ƒ The influence of austenite grain size on hot ductility of steel
ƒ Dispersion Strengthening.
ƒ Mechanical Alloying.
ƒ Solid Solution Strengthening.
ƒ Precipitation Hardening.

Chapter Two:
Effects of Alloying Elements on Iron Carbon Alloy

ƒ Introduction
ƒ Contributing factors to strength of steel.
ƒ Ways of improving strength of alloy steels.
ƒ Steels for special applications EF420 Lecture 7:
ƒ Cast Irons EF420 Lecture 9:
ƒ Ferrous Alloys EF420 Lecture 12:

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Page 2 of 180.

ƒ Alloying
ƒ Effects of alloying elements.
ƒ Relative effects in combinations
ƒ Characteristics of alloying element
ƒ Summary table.
ƒ Effects of alloying elements.
ƒ Effects of Alloying Elements on the Microstructures and Mechanical on ductile cast irons

ƒ Carbon.
ƒ Manganese.
ƒ Nickel.
ƒ Chromium.
ƒ Nickel & Chromium
ƒ Molybdenum.
ƒ Vanadium
ƒ Tungsten
ƒ Silicon
ƒ Copper
ƒ Phosphorous
ƒ Sulphur

ƒ Lead
ƒ Hydrogen
ƒ Selenium
ƒ Tantalum
ƒ Tin
ƒ Calcium
ƒ Cerium
ƒ Nitrogen
ƒ Boron
ƒ Aluminium
ƒ Zirconium
ƒ Niobium
ƒ Titanium
ƒ Cobalt
ƒ Tellurium

Chapter Three:
Articles on alloying elements in steel

ƒ Carbon contents, steel classification and alloy steels.
ƒ Carbon steels
ƒ Stainless steels
ƒ Strength in steels.
ƒ Alloying and its effects on the critical temperature and tensile strength.
ƒ Control of HSLA properties.
ƒ Influence of alloying elements on steel microstructures
ƒ Martensite in austenitic stainless steel welds.
ƒ Alloying effects on martensite, pearlite and bainite formation.
ƒ Steel alloys
ƒ Carbon steels to austenitic steels.
ƒ Selection of age-hardenable superalloys.
ƒ Metallurgy of Molybdenum in alloy steel and iron.
ƒ Maraging steels.
ƒ Periodic table and atomic radii.
ƒ 17-4PH precipitates hardening martensitic stainless steel.
ƒ Thermal Processing of Metal
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Page 3 of 180.
ƒ Thermal Processing of Metals
ƒ More reading.
ƒ Steel Making. 冶金视频
ƒ Additional reading:
ƒ Slag inclusion formation during solidification of Steel alloys and in cast iron.
ƒ Clean Steels.
ƒ Fundamental steps in thermomechanical processing of steels.
ƒ Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment.
ƒ Ion-nitriding of Maraging steel.
ƒ Microstructures and properties of low-alloy fire resistant steel.
ƒ Some fundamental steps in thermomechanical processing of steel.
ƒ Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment.
ƒ High Performance Copper-Precipitation-Hardened Steel.
ƒ Schaeffler diagram.
ƒ Comprehensive Characterization of Ageing Behavior in M250 Maraging Steel using Multi-NDE
Techniques.
ƒ Effect of Aging on Microstructure and Mechanical Property of 1900 MPa Grade Maraging Stainless
Steel.
ƒ Effect of aging conditions on Maraging Steels.
ƒ The influence of retained austenite on precipitation hardening of maraging steel.
ƒ 18Ni 马氏体时效钢时效机理的研究.
ƒ 1900MPa 级超高强度不锈钢的研制.
ƒ 固溶处理对新型马氏体时效不锈钢力学性能的影响.
ƒ 两种马氏体时效不锈钢的相变和力学性能.
ƒ 马氏体时效不锈钢的发展.
ƒ 马氏体时效不锈钢时效析出相及位向关系的研究.
ƒ 无钴马氏体时效钢的研究现状.
ƒ 无钴马氏体时效钢的研究与应用.
ƒ 新型CrCoNiMo 系马氏体时效不锈钢的强韧化机理.
ƒ 预先冷轧变形对马氏体时效钢强化的影响.
ƒ Control of High Strength Low Alloy Steel HSLA Properties by alloying
ƒ Brittle fracture 0f A105 flanges – EN10204 3.1B and shortfall












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Page 4 of 181.











Introduction to Dislocations, Fourth Edition by Derek Hull, D J Bacon
http://www.arab-eng.org/vb/t93373.html
The Science and Engineering of Materials by Donald R. Askeland
http://university.arabsbook.com/forum23/thread24766.html


Greek Alphabets.

1. Α α alpha
2. Β β beta
3. Γ γ gamma
4. Δ δ delta
5. Ε ε epsilon
6. Ζ ζ zeta
7. Η η eta
8. Θ θ theta
9. Ι ι iota
10. Κ κ kappa
11. Λ λ lamda
12. Μ μ mu
13. Ν ν nu
14. Ξ ξ xi
15. Ο ο omicron
16. Π π pi
17. Ρ ρ rho
18. Σ σ ς sigma
19. Τ τ tau
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Page 5 of 180.
Chapter One: The Mechanism of strengthening.

Elastic/Plastic Deformation
When a sufficient load is applied to a metal or other structural material, it will cause the material to change
shape. This change in shape is called deformation. A temporary shape change that is self-reversing after the
force is removed, so that the object returns to its original shape, is called elastic deformation. In other words,
elastic deformation is a change in shape of a material at low stress that is recoverable after the stress is
removed. This type of deformation involves stretching of the bonds, but the atoms do not slip past each other.
When the stress is sufficient to permanently deform
the metal, it is called plastic deformation. As
discussed in the section on crystal defects, plastic
deformation involves the breaking of a limited
number of atomic bonds by the movement of
dislocations. Recall that the force needed to break
the bonds of all the atoms in a crystal plane all at
once is very great. However, the movement of
dislocations allows atoms in crystal planes to slip
past one another at a much lower stress levels.
Since the energy required to move is lowest along
the densest planes of atoms, dislocations have a
preferred direction of travel within a grain of the
material. This results in slip that occurs along
parallel planes within the grain. These parallel slip
planes group together to form slip bands, which can
be seen with an optical microscope. A slip band
appears as a single line under the microscope, but it
is in fact made up of closely spaced parallel slip
planes as shown in the image.
Plastic deformation occurs when large numbers of dislocations move and multiply so as to result in
macroscopic deformation. In other words, it is the movement of dislocations in the material which allows for
deformation. If we want to enhance a material's mechanical properties (i.e. increase the yield and tensile
strength), we simply need to introduce a mechanism which prohibits the mobility of these dislocations.
Whatever the mechanism may be, (work hardening, grain size reduction, etc) they all hinder dislocation motion
and render the material stronger than previously.

The stress required to cause dislocation motion is orders of magnitude lower than the theoretical stress
required to shift an entire plane of atoms, so this mode of stress relief is energetically favorable. Hence, the
hardness and strength (both yield and tensile) critically depend on the ease with which dislocations move.
Pinning points, or locations in the crystal that oppose the motion of dislocations, can be introduced into the
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Page 6 of 180.
lattice to reduce dislocation mobility, thereby increasing mechanical strength.

Dislocations may be pinned due to stress field interactions with other dislocations and solute particles, or
physical barriers from grain boundaries and second phase precipitates. There are several strengthening
mechanisms for metals, however the key concept to remember about strengthening of metallic materials is that
it is all about preventing dislocation motion and propagation; you are making it energetically unfavorable for the
dislocation to move or propagate. For a material that has been strengthened, by some processing method, the
amount of force required to start irreversible (plastic) deformation is greater than it was for the original material.

In amorphous materials such as polymers, amorphous ceramics (glass), and amorphous metals, the lack of
long range order leads to yielding via mechanisms such as brittle fracture, crazing, and shear band formation.
In these systems, strengthening mechanisms do not involve dislocations, but rather consist of modifications to
the chemical structure and processing of the constituent material.

Unfortunately, strength of materials cannot infinitely increase. Each of the mechanisms elaborated below
involves some trade off by which other material properties are compromised in the process of strengthening.
Steel can be strengthened by several basic mechanisms, the most important of which are:
1. Work hardening or strain hardening.
2. Solid solution strengthening by interstitial atoms.
3. Solid solution strengthening by substitutional atoms.
4. Refinement of grain size.
5. Effects of heat treatment on microstructures.
6. Precipitation strengthening.
7. Grain boundary strengthening.
8. Dispersion strengthening, including lamellar and random dispersed structures.
The most distinctive aspect of strengthening of iron and steel is the role of the interstitial solutes carbon and
nitrogen. These elements also play a vital part in interacting with dislocations, and in combining preferentially
with some of the metallic alloying elements used in steels.
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Page 7 of 180.
Plastic Deformation: Mechanical Testing:

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http://www.slideshare.net/charliechong/09-castiron-presentation
http://mmd.sdsmt.edu/stress2.swf
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Page 8 of 180.
Understanding dislocations

Introduction to dislocations
http://www.msm.cam.ac.uk/doitpoms/tlplib/dislocations/printall.php


The Nature of Dislocations


Plastid deformation is a measure of material strength, plastic deformation is irreversible. Therefore, the
configuration of the atoms must be changed during plastic deformation, for otherwise they would return to their
original position on unloading. If we consider shearing a single crystal as an example, it can be deformed
plastically by sliding whole layers of atoms against each other as shown in figure above for this sliding to
happen, the bonds between the atoms have to be stretched elastically until they can switch to the next atom.
The stress required for this process can be estimated and is of the order of one fifth of the shear modulus of
the crystal. The yield strength predicted this way for metallic single crystals is thus between 1GPa and 25GPa.
If we measure the strength of single crystals of pure metals, the values found are several orders of magnitudes
below this theoretical value and even lie below that of engineering alloys. Typical values are in the range of a
few mega Pascal. As single crystals always contain lattice defects, one possible explanation could be that
these are responsible for the reduced strength. If, however, the number of defects is reduced further, for
instance by a heat treatment, the yield strength becomes even smaller. Only an absolutely perfect single
crystal without any defects would possess a yield strength agreeing with the theoretical prediction. This can
only be nearly realized in so-called whiskers, which, however, are extremely small. The reason for this
spectacular failure of the theoretical prediction is that plastic deformation does not occur by sliding of complete
layers of atoms. Instead, it proceeds by a mechanism that is based on a special type of lattice defect, the
dislocations. To understand plastic deformation of metals thus requires an understanding of dislocations.
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Page 9 of 180.

Dislocation densities
Dislocation is a lattice imperfection in a crystal structure which exerts a profound effect on a structure sensitive
properties such as strength, hardness, ductility and toughness. There are two types, edge and screw or
combination of both, all of which are characterized by a Burgers vector which represents the amount and
direction of slip when the dislocation moves. Click on the web links provided to read further.

Interaction of Dislocations

Transmission Electron Micrograph of Dislocations

Transmission Electron Micrograph of Dislocations
More reading:

http://en.wikipedia.org/wiki/Dislocation
http://www-sgrgroup.materials.ox.ac.uk/lectures/microplasticity.html

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Page 10 of 180.

"Atomistics" of edge dislocation motion and Asymmetry of screw and edge dislocation motion in Mo
Origins of Strength from Dislocation Dynamics

http://www.scribd.com/doc/7833526/12142005-Workshop
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Page 11 of 180.
Deformation and strengthening mechanisms


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http://www.scribd.com/doc/7833689/C7

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Page 12 of 180.
Crystal Defects

A perfect crystal, with every atom of the same type in the correct position, does not exist. All crystals have
some defects. Defects contribute to the mechanical properties of metals. In fact, using the term “defect” is sort
of a misnomer since these features are commonly intentionally used to manipulate the mechanical properties
of a material. Adding alloying elements to a metal is one way of introducing a crystal defect. Nevertheless, the
term “defect” will be used, just keep in mind that crystalline defects are not always bad. There are basic
classes of crystal defects:

ƒ point defects, which are places where an atom is missing or irregularly placed in the lattice structure.
Point defects include lattice vacancies, self-interstitial atoms, substitution impurity atoms, and interstitial
impurity atoms
ƒ linear defects, which are groups of atoms in irregular positions. Linear defects are commonly called
dislocations.
ƒ planar defects, which are interfaces between homogeneous regions of the material. Planar defects
include grain boundaries, stacking faults and external surfaces.

It is important to note at this point that plastic deformation in a material occurs due to the movement of
dislocations (linear defects). Millions of dislocations result for plastic forming operations such as rolling and
extruding. It is also important to note that any defect in the regular lattice structure disrupts the motion of
dislocation, which makes slip or plastic deformation more difficult. These defects not only include the point and
planer defects mentioned above, and also other dislocations. Dislocation movement produces additional
dislocations, and when dislocations run into each other it often impedes movement of the dislocations. This
drives up the force needed to move the dislocation or, in other words, strengthens the material. Each of the
crystal defects will be discussed in more detail in the following pages.

Point Defects

Point defects are where an atom is missing or is in an irregular place in the lattice structure. Point defects
include self interstitial atoms, interstitial impurity atoms, substitutional atoms and vacancies. A self interstitial
atom is an extra atom that has crowded its way into an interstitial void in the crystal structure. Self interstitial
atoms occur only in low concentrations in metals because they distort and highly stress the tightly packed
lattice structure.
A substitutional impurity atom is an atom of a different type than the bulk atoms, which has replaced one of the
bulk atoms in the lattice. Substitutional impurity atoms are usually close in size (within approximately 15%) to
the bulk atom. An example of substitutional impurity atoms is the zinc atoms in brass. In brass, zinc atoms with
a radius of 0.133 nm have replaced some of the copper atoms, which have a radius of 0.128 nm.
Interstitial impurity atoms are much smaller than the atoms in the bulk matrix. Interstitial impurity atoms fit into
the open space between the bulk atoms of the lattice structure. An example of interstitial impurity atoms is the
carbon atoms that are added to iron to make steel. Carbon atoms, with a radius of 0.071 nm, fit nicely in the
open spaces between the larger (0.124 nm) iron atoms.
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Page 13 of 180.
Vacancies are empty spaces where an atom should be, but is missing. They are common, especially at high
temperatures when atoms are frequently and randomly change their positions leaving behind empty lattice
sites. In most cases diffusion (mass transport by atomic motion) can only occur because of vacancies.


Linear Defects - Dislocations

Dislocations are another type of defect in crystals. Dislocations are areas were the atoms are out of position in
the crystal structure. Dislocations are generated and move when a stress is applied. The motion of dislocations
allows slip – plastic deformation to occur.
Before the discovery of the dislocation by Taylor, Orowan and Polyani in 1934, no one could figure out how the
plastic deformation properties of a metal could be greatly changed by solely by forming (without changing the
chemical composition). This became even bigger mystery when in the early 1900’s scientists estimated that
metals undergo plastic deformation at forces much smaller than the theoretical strength of the forces that are
holding the metal atoms together. Many metallurgists remained skeptical of the dislocation theory until the
development of the transmission electron microscope in the late 1950’s. The TEM allowed experimental
evidence to be collected that showed that the strength and ductility of metals are controlled by dislocations.

There are two basic types of dislocations, the edge dislocation and the screw dislocation. Actually, edge and
screw dislocations are just extreme forms of the possible dislocation structures that can occur. Most
dislocations are probably a hybrid of the edge and screw forms but this discussion will be limited to these two
types.
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Page 14 of 180.
Edge Dislocations
The edge defect can be easily visualized as an extra half-plane of atoms in a lattice. The dislocation is called a
line defect because the locus of defective points produced in the lattice by the dislocation lie along a line. This
line runs along the top of the extra half-plane. The inter-atomic bonds are significantly distorted only in the
immediate vicinity of the dislocation line.
Understanding the movement of a dislocation is key to understanding why dislocations allow deformation to
occur at much lower stress than in a perfect crystal. Dislocation motion is analogous to movement of a
caterpillar. The caterpillar would have to exert a large force to move its entire body at once. Instead it moves
the rear portion of its body forward a small amount and creates a hump. The hump then moves forward and
eventual moves all of the body forward by a small amount.


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Page 15 of 180.
As shown in the set of images above, the dislocation moves similarly moves a small amount at a time. The
dislocation in the top half of the crystal is slipping one plane at a time as it moves to the right from its position in
image (a) to its position in image (b) and finally image (c). In the process of slipping one plane at a time the
dislocation propagates across the crystal. The movement of the dislocation across the plane eventually causes
the top half of the crystal to move with respect to the bottom half. However, only a small fraction of the bonds
are broken at any given time. Movement in this manner requires a much smaller force than breaking all the
bonds across the middle plane simultaneously.
Screw Dislocations
There is a second basic type of dislocation, called screw
dislocation. The screw dislocation is slightly more
difficult to visualize. The motion of a screw dislocation is
also a result of shear stress, but the defect line
movement is perpendicular to direction of the stress and
the atom displacement, rather than parallel. To visualize
a screw dislocation, imagine a block of metal with a
shear stress applied across one end so that the metal
begins to rip. This is shown in the upper right image.
The lower right image shows the plane of atoms just
above the rip. The atoms represented by the blue
circles have not yet moved from their original position.
The atoms represented by the red circles have moved
to their new position in the lattice and have
reestablished metallic bonds. The atoms represented
by the green circles are in the process of moving. It can
be seen that only a portion of the bonds are broke at
any given time. As was the case with the edge
dislocation, movement in this manner requires a much
smaller force than breaking all the bonds across the
middle plane simultaneously.
If the shear force is increased, the atoms will continue to
slip to the right. A row of the green atoms will find there way back into a proper spot in the lattice (and become
red) and a row of the blue atoms will slip out of position (and become green). In this way, the screw dislocation
will move upward in the image, which is perpendicular to direction of the stress. Recall that the edge
dislocation moves parallel to the direction of stress. As shown in the image below, the net plastic deformation
of both edge and screw dislocations are the same, however.
The dislocations move along the densest planes of atoms in a material, because the stress needed to move
the dislocation increases with the spacing between the planes. FCC and BCC metals have many dense planes,
so dislocations move relatively easy and these materials have high ductility. Metals are strengthened by
making it more difficult for dislocations to move. This may involve the introduction of obstacles, such as
interstitial atoms or grain boundaries, to “pin” the dislocations. Also, as a material plastically deforms, more
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Page 16 of 180.
dislocations are produced and they will get into each others way and impede movement. This is why strain or
work hardening occurs.
In ionically bonded materials, the ion must move past an area with a repulsive charge in order to get to the next
location of the same charge. Therefore, slip is difficult and the materials are brittle. Likewise, the low density
packing of covalent materials makes them generally more brittle than metals.


Planar Defects

Stacking Faults and Twin Boundaries
A disruption of the long-range stacking sequence can produce two other common types of crystal defects: 1) a
stacking fault and 2) a twin region. A change in the stacking sequence over a few atomic spacing produces a
stacking fault whereas a change over many atomic spacing produces a twin region.

A stacking fault is a one or two layer interruption in the stacking sequence of atom planes. Stacking faults
occur in a number of crystal structures, but it is easiest to see how they occur in close packed structures. For
example, it is know from a previous discussion that face centered cubic (fcc) structures differ from hexagonal
close packed (hcp) structures only in their stacking order. For hcp and fcc structures, the first two layers
arrange themselves identically, and are said to have an AB arrangement. If the third layer is placed so that its
atoms are directly above those of the first (A) layer, the stacking will be ABA. This is the hcp structure, and it
continues ABABABAB. However it is possible for the third layer atoms to arrange themselves so that they are
in line with the first layer to produce an ABC arrangement which is that of the fcc structure. So, if the hcp
structure is going along as ABABAB and suddenly switches to ABABABCABAB, there is a stacking fault
present.
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Page 17 of 180.
Alternately, in the fcc arrangement the pattern is ABCABCABC. A stacking fault in an fcc structure would
appear as one of the C planes missing. In other words the pattern would become ABCABCAB_ABCABC.
If a stacking fault does not corrects itself immediately but continues over some number of atomic spacing, it will
produce a second stacking fault that is the twin of the first one. For example if the stacking pattern is
ABABABAB but switches to ABCABCABC for a period of time before switching back to ABABABAB, a pair of
twin stacking faults is produced. The red region in the stacking sequence that goes
ABCABCACBACBABCABC is the twin plane and the twin boundaries are the A planes on each end of the
highlighted region.
Grain Boundaries in Polycrystals
Another type of planer defect is the grain boundary. Up to this point, the discussion has focused on defects of
single crystals. However, solids generally consist of a number of crystallites or grains. Grains can range in size
from nanometers to millimeters across and their orientations are usually rotated with respect to neighboring
grains. Where one grain stops and another begins is know as a grain boundary. Grain boundaries limit the
lengths and motions of dislocations. Therefore, having smaller grains (more grain boundary surface area)
strengthens a material. The size of the grains can be controlled by the cooling rate when the material cast or
heat treated. Generally, rapid cooling produces smaller grains whereas slow cooling result in larger grains. For
more information, refer to the discussion on solidification.

Bulk Defects

Bulk defects occur on a much bigger scale than the rest of
the crystal defects discussed in this section. However, for
the sake of completeness and since they do affect the
movement of dislocations, a few of the more common bulk
defects will be mentioned. Voids are regions where there
are a large number of atoms missing from the lattice. The
image to the right is a void in a piece of metal The image
was acquired using a Scanning Electron Microscope
(SEM). Voids can occur for a number of reasons. When
voids occur due to air bubbles becoming trapped when a
material solidifies, it is commonly called porosity. When a
void occurs due to the shrinkage of a material as it
solidifies, it is called cavitation.
Another type of bulk defect occurs when impurity atoms cluster together to form small regions of a different
phase. The term ‘phase’ refers to that region of space occupied by a physically homogeneous material. These
regions are often called precipitates. Phases and precipitates will be discussed in more detail latter.
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Page 18 of 180.

Pinning points - overview.

In a crystalline material, a dislocation is capable of traveling throughout the lattice when relatively small
stresses are applied. This movement of dislocations results in the material plastically deforming. Pinning points
in the material act to halt a dislocation's movement, requiring a greater amount of force to be applied to
overcome the barrier. This results in an overall strengthening of materials.
Types of pinning points

Point defects

Point defects (as well as stationary dislocations, jogs, and kinks) present in a material create stress fields
within a material that disallow traveling dislocations to come into direct contact. Much like two particles of the
same electric charge feel a repulsion to one another when brought together, the dislocation is pushed away
from the already present stress field.
Alloying elements

The introduction of atom
1
into a crystal of atom
2
creates a pinning point for multiple reasons. An alloying atom
is by nature a point defect, thus it must create a stress field when placed into a foreign crystallographic position,
which could block the passage of a dislocation. However, it is possible that the allowing material is
approximately the same size as the atom that is replaced, and thus its presence would not stress the lattice (as
occurs in cobalt alloyed nickel). The different atom would, though, have a different elastic modulus, which
would create a different terrain for the moving dislocation. A higher modulus would look like an energy barrier,
and a lower like an energy trough – both of which would stop its movement.
Second phase precipitates


The precipitation of a second phase within the lattice of a material creates physical blockades through
which a dislocation cannot pass. The result is that the dislocation must bend (which requires greater
energy, or a greater stress to be applied) around the precipitates, which inevitably leaves residual
dislocation loops encircling the second phase material and shortens the original dislocation. This is a
schematic shows how a dislocation interacts with solid phase precipitates. The dislocation moves from
left to right in each frame.
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Page 19 of 180.


Dislocation slip mechanism

Grain boundaries

Dislocations require proper lattice ordering to move through a material. At grain boundaries, there is a lattice
mismatch, and every atom that lies on the boundary is uncoordinated. This stops dislocations that encounter
the boundary from moving.


Dislocations in motion
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Page 20 of 180.

Methods of strengthening

Following are brief description s on the methods of strengthening.

Work or Strain hardening

The reason for strain hardening is that the dislocation density increases with plastic deformation (cold work)
due to multiplication. The average distance between dislocations then decreases and dislocations start
blocking the motion of dislocations.
The primary species responsible for work hardening are dislocations. Dislocations interact with each other by
generating stress fields in the material. The interaction between the stress fields of dislocations can impede
dislocation motion by repulsive or attractive interactions. Additionally, if two dislocations cross, dislocation line
entanglement occurs, causing the formation of a jog which opposes dislocation motion. These entanglements
and jogs act as pinning points, which oppose dislocation motion. As both of these processes are more likely to
occur when more dislocations are present, there is a correlation between dislocation density and yield
strength,


Where G is the shear modulus, b is the Burgers vector, and is the dislocation density.

Increasing the dislocation density increases the yield strength which results in a higher shear stress required to
move the dislocations. This process is easily observed while working a material. Theoretically, the strength of a
material with no dislocations will be extremely high (τ=G/2) because plastic deformation would require the
breaking of many bonds simultaneously. However, at moderate dislocation density values of around 107-109
dislocations/m2, the material will exhibit a significantly lower mechanical strength. Analogously, it is easier to
move a rubber rug across a surface by propagating a small ripple through it than by dragging the whole rug. At
dislocation densities of 1014 dislocations/m2 or higher, the strength of the material becomes high once again.
It should be noted that the dislocation density can't be infinitely high because then the material would lose its
crystalline structure.

Work hardening is an important strengthening process in steel, particularly in obtaining high strength levels in
rod and wire, both in plain carbon and alloy steels. For example, the tensile strength of a 0.05% C steel
subjected to 95% reduction in area by wire drawing, is raised by no less than 550 MPa while higher carbon
steels are strengthened by up to twice this amount. Indeed, without the addition of special alloying elements,
plain carbon steels can be raised to strength levels above 1500 MPa simply by the phenomenon of work
hardening.
Basic work on the deformation of iron has largely concentrated on the other end of the strength spectrum,
namely pure single crystals and polycrystals subjected to small controlled deformations. The diversity of slip
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Page 21 of 180.
planes leads to rather irregular wavy slip bands in deformed crystals, as the dislocations can readily move from
one type of plane to another by cross slip, provided they share a common slip direction.
The yield stress of iron single crystals are very sensitive to both temperature and strain rate and a similar
dependence has been found for less pure polycrystalline iron. Therefore, the temperature sensitivity cannot be
attributed to interstitial impurities. It is explained by the effect of temperature on the stress needed to move free
dislocations in the crystal, the Peierls-Nabarro stress.
Case Study 1: The effect of cyclic torsion on the dislocation structure of drawn mild steel
1. Introduction
Cold forming of metals usually causes their work hardening. The magnitude of this hardening depends on the
area reduction, on the temperature and strain rate associated with the processing, and on the way the strain is
imposed on the metal. Keeping all other variables constant, the work hardening of a metal submitted to a
sequential straining under varying directions or of different natures is different from that resulting from
monotonic straining. Changes in the way the material is deformed can alter the hardening rates and even
cause strain softening of the metal1-16.
Recent research results17-19 show that cyclic straining influences in various ways the mechanical behavior of
annealed and drawn metal bars. Annealed Aluminum submitted to cyclic torsion displays higher flow stresses
than the annealed material. On the other hand, cyclic torsion softens previously drawn Aluminum. Cyclic
torsion also softens steel bars previously drawn in one or two passes and hardens the initially annealed
material. Experimental results indicate that the stress-strain curve and the work hardening coefficient (n) of
steel drawn in two passes and submitted to cyclic torsion are similar to those for the material submitted to only
one drawing pass. This is similar to the case of the Aluminum alloy 6063, where the cyclic torsion after two
drawing passes eliminates the hardening associated with the second drawing pass. It is also observed for both
materials that their Ultimate Tensile Strength (UTS) tends to remain unaltered by cyclic torsion, in the case of
initially annealed material, whereas their Yield Strength (YS) is considerably increased by cyclic torsion. The
YS and UTS of both previously drawn materials are decreased by cyclic torsion, with the exception of the YS of
Aluminum drawn in a single pass. The decrease in these properties is more pronounced after two drawing
passes than after a single drawing pass. Finally, cyclic torsion increases the Tensile Elongation to Fracture of
drawn material and decreases this property for initially annealed material.
The present research analyzes the relationship between the mechanical effects described above and the
dislocation structures in Low Carbon steel.

2. Materials and Experimental Methods
The material was an AISI 1010 steel with the following chemical composition: 0.12%C, 0.47%Mn, 0.07%Si,
0.003%Sn, 0.01%Mo, 0.016%P e 0.013%S, received as cylindrical bars 6.4 mm in diameter. The bars were
initially annealed and some of them were drawn in one or two passes. A fraction of these bars were then
submitted to cyclic torsion. The effects of the strain path were analyzed by Transmission Electron Microscopy
(TEM).
Annealing was performed under vacuum, at 850 °C for 2400 seconds, leading to an average hardness of
122.6 HV. Drawing was performed in a hydraulic draw bench, using Tungsten Carbide dies with semi-angle of
8?and abundant lubrication with a Molybdenum Disulfide paste. Different dies were employed, guaranteeing a
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Page 22 of 180.
fixed reduction of area of 20% in each pass. Cyclic torsion (11.2% plastic strain per cycle, total of 10 cycles)
was performed in an especially adapted lathe, where the chuck was manually actuated. All experiments were
performed at room temperature, at a strain rate of 0.002 / s5. All deformed samples were stored at
temperatures below 0 °C in order to avoid static strain aging effects.
TEM was performed in a JEOL-JEM microscope, operated at 200 kV. Analyses were performed in 3 mm
samples taken from the cross-section of the bars. Sample preparation involved initial mechanical polishing,
followed by electrolytic thinning with a perchloric acid and ethanol solution at room temperature.

3. Results and Discussion
The dislocation structures of the annealed and of the drawn material (in one or two passes) are shown in
Figures 1 and The effect of cyclic torsion on the dislocation structure of drawn mild steel2 respectively. The
dislocation density is quite low for the annealed material, whereas the deformed material displays a much
higher dislocation density. Drawn material shows an aligned cell structure, with irregular cell sizes and cell wall
thickness. Dense dislocation networks can be observed inside the cells. Higher drawing strains lead to a
smaller cell size, as expected.

Figure 1.

Figure 2a.
Figure 2b. TEM of annealed and drawn steel
(8% and 20% per pass) a: 1 pass b: 2 passes
.

The dislocation structure of the material submitted only to cyclic torsion is broadly similar to that resulting from
drawing (see Figure 3), but the cell size is higher and the tendency to cell alignment is less pronounced than in
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Page 23 of 180.
drawing. It is important to realize that the total strain caused by cyclic torsion is much higher than in drawing,
but leads to essentially similar dislocation structures.

The analysis of Figure 4 indicates that the dislocation structure of the material after one drawing pass is altered
by subsequent cyclic torsion. There is an increase in the cell size, a decrease in their alignment and in the
dislocation density within the cells, and an overall evolution of alignment in only one direction to a
"checkerboard" appearance, which is typical of the development of two sets of aligned cells, corresponding to
the two directions of twisting. This is also the situation for the material initially annealed, drawn in 2 passes and
cyclically twisted (Figure 5). Under these circumstances, the dislocation cells tend to be larger and the
dislocation density inside the cells lower than for one drawing pass followed by cyclic torsion. Cyclic torsion
promotes dynamic recovery of the material, involving the annihilation of cell walls and the decrease of
dislocation density inside the cells. This is similar to results from the analysis of the Bauschinger effect20.
where such dislocation annihilation stems from dislocation movements in opposing directions.



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Page 24 of 181.

Considering the widely established relationship between the material flow stress G, and the corresponding
dislocation density r20:

one should expect higher flow stresses in the drawn or cyclic twisted material than in the annealed material.
On the other hand, the recovery promoted by cyclic torsion of the previously drawn material should lead to their
softening and consequent lower flow stresses.

4. Conclusions
Drawing of low carbon steel leads to the formation of an aligned dislocation structure, displaying irregular cell
sizes and cell wall thickness as well as dense networks of dislocations inside the cells.
Cyclic torsion promotes the softening of material previously strained by drawing. This softening is associated
with a restructuring of the previous dislocation arrangement, involving an increase in cell size, a decrease in
the dislocation density inside the cells and a "checkerboard" dislocation wall structure.


Strain Hardening and Annealing Slide Show: Full download

http://www.slideshare.net/charliechong/askeland-phule-notes-ch12-printable-presentation

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Page 25 of 180.
Dislocation and Plastic Deformation:

http://www.slideshare.net/charliechong/chapter05-1-presentation

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Page 26 of 180.
Grain Boundary Strengthening


In grain boundary strengthening the grain boundaries act as pinning points impeding further dislocation
propagation. Since the lattice structure of adjacent grains differs in orientation, it requires more energy for a
dislocation to change directions and move into the adjacent grain. The grain boundary is also much more
disordered than inside the grain, which also prevents the dislocations from moving in a continuous slip plane.
Impeding this dislocation movement will hinder the onset of plasticity and hence increase the yield strength of
the material.

Grain boundaries act as an impediment to dislocation motion for the following two reasons:

• Dislocation must change its direction of motion due to the differing orientation of grains.
• Discontinuity of slip planes from grain 1 to grain

Under an applied stress, existing dislocations and dislocations generated by Frank-Read Sources will move
through a crystalline lattice until encountering a grain boundary, where the large atomic mismatch between
different grains creates a repulsive stress field to oppose continued dislocation motion. As more dislocations
propagate to this boundary, dislocation 'pile up' occurs as a cluster of dislocations are unable to move past the
boundary. As dislocations generate repulsive stress fields, each successive dislocation will apply a repulsive
force to the dislocation incident with the grain boundary. These repulsive forces act as a driving force to reduce
the energetic barrier for diffusion across the boundary, such that additional pile up causes dislocation diffusion
across the grain boundary, allowing further deformation in the material.

Decreasing grain boundary size decreases the amount of possible pile up at the boundary, increasing the
amount of applied stress necessary to move a dislocation across a grain boundary. The higher the applied
stress to move the dislocation, the higher the yield strength. Thus, there is then an inverse relationship
between grain boundary size and yield strength, as demonstrated by the Hall-Petch equation. A lower number
of dislocations per grain results in a lower dislocation 'pressure' building up at grain boundaries. This makes it
more difficult for dislocations to move into adjacent grains. This relationship can be mathematically described
as follows:
,
Where k is a constant, d is the average grain diameter and σy,0 is the original yield stress.
However, when there is a large direction change in the orientation of the two adjacent grains, the dislocation
may not necessarily move from one grain to the other but instead create a new source of dislocation in the
adjacent grain. The theory remains the same that more grain boundaries create more opposition to dislocation
movement and in turn strengthens the material.

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Page 27 of 180.


Figure 1: Hall-Petch Strengthening is limited by the size of dislocations. Once the grain size reaches
about 10 nm, grain boundaries start to slide.

Obviously, there is a limit to this mode of strengthening, as infinitely strong materials do not exist. Grain
boundary sizes can range from about 100 μm (large grains) to 1 μm (small grains). Lower than this, the size of
dislocations begins to approach the size of the grains. At a grain size of about 10 nm, only one or two
dislocations can fit inside of a grain (see Figure 1 above). This scheme prohibits dislocation pile-up and never
results in grain boundary diffusion. The lattice resolves the applied stress by grain boundary sliding, resulting in
a decrease in the material's yield strength; A phenomenon known as grain-boundary sliding.

To understand the mechanism of grain boundary strengthening one must understand the nature of
dislocation-dislocation interactions. Dislocations create a stress field around them given by:
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Page 28 of 180.
,
Where G is the material's shear modulus, and b is the Burgers vector. If the dislocations are in the right
alignment with respect to each other, the local stress fields they create will repel each other. This helps
dislocation movement along grains and across grain boundaries. Hence, the more dislocations are present in a
grain, the greater the stress field felt by a dislocation near a grain boundary:




This is a schematic roughly illustrating the concept of dislocation pile up and how it effects the strength of
the material. A material with larger grain size is able to have more dislocation to pile up leading to a bigger
driving force for dislocations to move from one grain to another. Thus you will have to apply less force to
move a dislocation from a larger than from a smaller grain, leading materials with smaller grains to exhibit
higher yield stress.

In a polycrystalline metal, grain size has a tremendous influence on the mechanical properties. Because grains
usually have varying crystallographic orientations, grain boundaries arise. While an undergoing deformation,
slip motion will take place.

The refinement of the grain size of ferrite provides one of the most important strengthening routes in the heal
treatment of steels. The grain size effect on the yield stress can therefore be explained by assuming that a
dislocation source operates within a crystal causing dislocations to move and eventually to pile up at the grain
boundary. The pile-up causes a stress to be generated in the adjacent grain, which, when it reaches a critical
value, operates a new source in that grain.
In this way, the yielding process is propagated from grain to grain. The grain size determines the distance
dislocations have to move to form grain boundary pile-ups, and thus the number of dislocations involved. With
large grain sizes, the pile-ups will contain larger numbers of dislocations, which will in turn cause higher stress
concentrations in neighboring grains.
In practical terms, the finer the grain size, the higher the resulting yield stress and, as a result, in modern steel
working much attention is paid to the final ferrite grain size. While a coarse grain size of d-1/2 = 2, i.e. d = 0.25
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Page 29 of 180.
mm, gives a yield stress in mild steels of around 100 MPa, grain refinement to d-1/2 = 20. i.e. d = 0.0025 mm,
raises the yield stress to over 500 MPa, so that achieving grain sizes in the range 2-10 μm is extremely
worthwhile.

The effect of grain size on yield strength,
y
, is given by the Hall Petch equation for structural steels:

where
o
is the lattice resistance, i.e. friction stress which opposes dislocation motion
k is a constant, sometimes called the dislocation locking term
d is the ferrite grain size

14 µm
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More reading:
Effect of Microstructure on Mechanical Properties of High Strength Steel Weld Metals
Effects of Tempering on the Microstructure and Mechanical Properties of Low Carbon, Low Alloy Martensitic Steel
Effect of Microstructural Variation on Weld Metal Cold Cracking of HSLA-100 Steel

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Page 30 of 180.

Effect of Microstructure Refinement on the Strength and Toughness of low alloy martensitic
steel
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http://www.scribd.com/doc/7824864/Effect-of-Micro-Structure-Refinement-on-the-Strength-and-Toughness-of-
Low-Alloy-Martensitic-Steel

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Page 31 of 180.

Effect of microstructure and notches on the fracture toughness of medium carbon steel
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Page 32 of 180.

The influence of austenite grain size on hot ductility of steel
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http://www.scribd.com/doc/7825091/The-Influence-of-Austenite-Grain-Size-on-Hot-Ductility-of-Steel

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Page 33 of 180.
Dispersion Strengthening

(Mechanical Alloying)
Dispersion strengthening is about the interaction between dislocations and finely dispersed particles in the
metal matrix. Traditionally, dispersion particles are obtained as precipitates from phase transformations during
traditional metallurgical processes (melting, solidification, and heat treating). This is the case of many
high-strength commercial alloys. However, maximum service temperatures are limited by the limited thermal
stability of particles or precipitates obtained from thermal processes.

A: Lattice distortion due to the presence of coherent precipitate:
B: Noncohereny precipitates produce no lattice distortion

Particles, which may not be metallurgical compatible with a given metal, can be introduced in a metal matrix by
violently deforming mixtures of different powders. Such technique is called mechanical alloying . An example is
high-energy ball milling. Using this technique, oxides and other highly stable chemical species can be
introduced uniformly into the metal microstructure. A further refinement of this technique allows oxidation and
other chemical reactions to take place during the mixing process, a technique that allegedly promotes the
formation of ultrafine dispersoids as well as allowing control of particle composition and distribution. After
mixing, the powder mixture can then be consolidated and compacted using a number of powder metallurgy
techniques to produce a solid with a very fine grain structure.
Mechanical alloying methods permit the manufacturing of metallic alloys with a number of interesting
properties. Some examples of materials include nanocrystalline and amorphous materials, metastable phases,
and alloys with extended solubility limits. Mechanical alloying was originally developed as a means of raising
the maximum service temperatures of nickel-based superalloys for aircraft gas-turbine applications. As turbine
operating temperatures rose, so too did the demand for materials with increased high-temperature strength
and oxidation resistance. Mechanical alloying avoids many of the problems associated with conventional
melting and solidification processes, and is now used to make a variety of oxide-dispersion-strengthened
(ODS) Fe-Cr, Ni-Cr, and Ni-Cr-gamma superalloys for turbine-engine industrial applications and aluminum
alloys for aircraft structural components. Mechanical alloying may play a key role in the development of future
aerospace systems by enabling the production of even higher performance materials that are difficult or
impossible to make by other methods.
The effectiveness of dispersion strengthening largely depends on (a) mechanical and geometrical
characteristics of the dispersoids, such as hardness, continuity, size, and shape, and (b) their density and
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Page 34 of 180.
distribution (dispersion factor) in the metal matrix. By controlling process parameters, such as characteristics
of the raw powder materials, pressing pressures, atmospheres, cycle time, and temperatures, the
microstructure (e.g., grain size, dispersion size, volume fraction, and distribution) can be tailored for specific
performance requirements. New research initiatives in this field include the synthesis of refractory carbide
nanoparticles and assessment of their use as dispersion strengthening agents, as well as alternative methods
to inoculate the metal matrix.

In all steels there is normally more than one phase present, and indeed it is often the case that several phases
can be recognized in the microstructure. The matrix, which is usually ferrite (bcc structure) or austenite (fcc
structure) strengthened by grain size refinement and by solid solution additions, is further strengthened, often
to a considerable degree, by controlling the dispersions of the other phases in the microstructure. The
commonest other phases are carbides formed as a result of the low solubility of carbon in α-iron. In plain
carbon steels this carbide is normally Fe3C (cementite), which can occur, in a wide range of structures from
coarse lamellar form (pearlite), to fine rod or spheroidal precipitates (tempered steels). In alloy steels, the
same range of structures is encountered, except that in many cases iron carbide is replaced by other carbides,
which are thermodynamically more stable. Other dispersed phases which are encountered include nitrides,
intermetallic compounds, and, in cast irons, graphite.
Most dispersions lead to strengthening, but often they can have adverse effects on ductility and toughness. In
fine dispersions (where ideally small spheres are randomly dispersed in a matrix) are well-defined
relationships between the yield stress, or initial flow stress, and the parameters of the dispersion.
These relationships can be applied to simple dispersions sometimes found in steels, particularly after
tempering, when, in plain carbon steels, the structure consists of spheroidal cementite particles in a ferritic
matrix. However, they can provide approximations in less ideal cases, which are the rule in steels, where the
dispersions vary over the range from fine rods and plates to irregular polyhedral. Perhaps the most familiar
structure in steels is that of the eutectoid pearlite, usually a lamellar mixture of ferrite and cementite. This can
be considered as an extreme form of dispersion of one phase in another, and undoubtedly provides a useful
contribution to strengthening.


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General behaviour of the powder particles during mechanical alloying processing


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http://www.scribd.com/doc/7823923/Mechanical-Alloy

Case Study:

Effect of mechanical alloying and Ti addition on solution and ageing treatment of an AA7050 aluminium alloy
http://www.scielo.br/scielo.php?pid=S1516-14392007000200017&script=sci_arttext
Mechanical Alloys & Milling
http://www.scribd.com/doc/3629131/Mechanical-alloying-and-milling-Suryanarayana
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Page 37 of 180.
Solid solution strengthening




This is a schematic illustrating how the lattice is strained by the addition of substitutional and interstitial solute.
Notice the strain in the lattice that the solute atoms cause. The interstitial solute could be carbon in iron for
example. The carbon atoms in the interstitial sites of the lattice create a stress field that impedes dislocation
movement.
http://en.wikipedia.org/wiki/Strengthening_mechanisms_of_materials

A grain boundary in a 2D lattice is the interface between two regions of crystalline order. Each region or 'grain'
has a different orientation with respect to some arbitrary axis perpendicular to the plane of the lattice.

Grain boundaries

A vacancy is a point defect that arises when an atom is 'missing' from the ideal crystal structure.

A vacancy
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A solute atom in a crystal structure is an atomic species that is different from the majority of atoms that form the
structure. Solute atoms of similar size to those in the host lattice may substitute for host atoms - these are
known as substitutional solutes. Solute atoms that are much smaller than the host atoms may exist within
normally empty regions (interstices) in the host lattice, where they are called interstitial solutes.

Substitutional and interstitial solutes.
Note that some distortion of the host lattice occurs around the solutes. A dislocation in a 2D close-packed
plane can be described as an extra 'half-row' of atoms in the structure. Dislocations can be characterised by
the Burgers vector which gives information about the orientation and magnitude of the dislocation.

Dislocation
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Page 39 of 180.

Metal Crystal Structure Atomic Radius (nm)
Aluminum FCC 0.1431
Cadmium HCP 0.1490
Chromium BCC 0.1249
Cobalt HCP 0.1253
Copper FCC 0.1278
Gold FCC 0.1442
Iron (Alpha) BCC 0.1241
Lead FCC 0.1750
Magnesium HCP 0.1599
Molybdenum BCC 0.1363
Nickel FCC 0.1246
Platinum FCC 0.1387
Silver FCC 0.1445
Tantalum BCC 0.1430
Titanium (Alpha) HCP 0.1445
Tungsten BCC 0.1371
Zinc HCP 0.1332
A nanometer (nm) equals 10
-9
meter or 10 Angstrom units.





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Page 40 of 180.
Solid solution strengthening by interstitials

The formation of interstitial atmospheres at dislocations requires diffusion of the solute. As both carbon and
nitrogen diffuse much more rapidly in iron than substitutional solutes, it is not surprising that strain ageing can
take place readily in the range from 20°C to 150°C. Consequently the atmosphere condenses to form rows of
interstitial atoms along the cores of the dislocations. These arise because the temperature is high enough to
allow interstitial atoms to diffuse during deformation, and to form atmospheres around dislocations generated
throughout the stress-strain curve. Steels tested under these conditions also show low ductility, due partly to
the high dislocation density and partly to the nucleation of carbide particles on the dislocations where the
carbon concentration is high. The phenomenon is often referred to as blue brittleness, blue being the
interference color of the steel surface when oxidized in this temperature range.
The break away of dislocations from their carbon atmospheres as a cause of the sharp yield point became a
controversial aspect of the theory because it was found that the provision of free dislocations, for example, by
scratching the surface of a specimen, did not eliminate the sharp yield point. An alternative theory was
developed which assumed that, once condensed carbon atmospheres are formed in iron, the dislocations
remain locked, and the yield phenomena arise from the generation and movement of newly formed
dislocations.
To summarize, the occurrence of a sharp yield point depends on the occurrence of a sudden increase in the
number of mobile dislocations. However, the precise mechanism by which this takes place will depend on the
effectiveness of the locking of the pre-existing dislocations. If the pinning is weak, then the yield point can arise
as a result of unpinning. However, if the dislocations are strongly locked, either by interstitial atmospheres or
precipitates, the yield point will result from the rapid generation of new dislocations.
Under conditions of dynamic strain ageing, where atmospheres of carbon atoms form continuously on
newly-generated dislocations, it would be expected that a higher density of dislocations would be needed to
complete the deformation, if it is assumed that most dislocations which attract carbon atmospheres are
permanently locked in position.


Strengthening at high interstitial concentrations


Austenite can take into solid solution up to 10% carbon, which can be retained in solid solution by rapid
quenching. However, in these circumstances the phase transformation takes place, not to ferrite but to a
tetragonal structure referred to as martensite. This phase forms as a result of diffusion less shear
transformation leading to characteristic laths or plates.
If the quench is sufficiently rapid, the martensite is essentially a supersaturated solid solution of carbon in a
tetragonal iron matrix, and as the carbon concentration can be greatly in excess of the equilibrium
concentration in ferrite, the strength is raised very substantially. High carbon martensites are normally very
hard but brittle, the yield strength reaching as much as 1500 MPa; much of this increase can be directly
attributed to increased interstitial solid solution hardening, but there is also a contribution from the high
dislocation density, which is characteristic of martensitic transformations in iron-carbon alloys.

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Substitutional solid solution strengthening of iron


Many metallic elements form solid solutions in γ- and α-iron. These are invariably substitutional solid solutions,
but for a constant atomic concentration of alloying elements there are large variations in strength. Using single
crystal data for several metals, Fig. 1 shows that an element such as vanadium has a weak strengthening
effect on α-iron at low concentrations (< 2%), while silicon and molybdenum are much more effective
strengthened. Other data indicates that phosphorus; manganese, nickel and copper are also effective
strengtheners. However, it should be noted that the relative strengthening might alter with the temperature of
testing, and with the concentrations of interstitial solutes present in the steels.

Figure 1. Solid solution strengthening of iron crystals by substitutional solutes. Ratio of the critical resolved shear stress τ0
to shear modulus μ as a function of atomic concentration.

The strengthening achieved by substitutional solute atoms is, in general, greater the larger the difference in
atomic size of the solute from that of iron, applying the Hume-Rothery size effect. However, from the work of
Fleischer and Takeuchi it is apparent that differences in the elastic behavior of solute and solvent atoms are
also important in determining the overall strengthening achieved.
In practical terms, the contribution to strength from solid solution effects is superimposed on hardening from
other sources, e.g. grain size and dispersions. Also it is a strengthening increment, like that due to grain size,
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Page 42 of 180.
which need not adversely affect ductility. In industrial steels, solid solution strengthening is a far from negligible
factor in the overall strength, where it is achieved by a number of familiar alloying elements, e.g. manganese,
silicon, nickel, molybdenum, several of which are frequently present in a particular steel and are additive in
their effect. These alloying elements arc usually added for other reasons, e.g. Si to achieve deoxidation, Mn to
combine with sulphur or Mo to promote hardenability. Therefore, the solid solution hardening contribution can
be viewed as a useful bonus.

Effect of solid solution strengthening


The graph below shows how different alloying additions affect the yield strength of a ferrite + pearlite structural
steel.

Quiz
1. C and N are interstitial elements rather than substitutional.
2. C and N are much bigger atoms hence introduce more strain energy.
3. C and N have a much smaller atomic mass number therefore for the same weight % addition you are
adding a higher atomic %.
4. Mn and Mo have much lower diffusivities in steel therefore cannot pin the moving dislocations.

1. and 3. - correct, interstitial elements tend to produce a greater strengthening effect because they cause
more strain in the lattice than substitutional elements in steels. The fact that C and N have a smaller atomic
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Page 43 of 180.
mass number does mean that for the same weight % addition there are more C or N atoms introduced into the
steel and hence more lattice strain
Iron and Its Interstitial Solid Solutions

DESCRIPTION
Iron, a silvery white solid metal, appears in Group VIII of the periodic table as a transition element. Its atomic
number is 26, and its atomic weight is 55.847. Iron is notable among the elements in the abundance of its ores
and the vast number of useful alloys that can be formulated with iron as the major constituent. Iron is also
biologically important.

In its pure form, iron is rather soft and is malleable and ductile at room temperature. It melts at 1,535 deg C and
boils at 3,000 deg C. Pure iron can exist in two structural types, or allotropic forms. At room temperature the
iron atoms are arranged in a body-centered cubic lattice called the a-form, which is transformed at 910 deg C
into a cubic close-packed structure called the gamma-form. At 1,390 deg C iron returns to a body-centered
cubic structure, called the delta-form.

APPLICATION

Iron is abundant and easily obtainable from its ores. Its desirable mechanical and magnetic properties, as well
as its resistance to corrosion, may be improved by mixing iron with other elements, frequently metals, to form
alloys.

Perhaps the most important alloy of iron is steel, which contains up to approximately 2% carbon. Steels that
contain about 0.25% carbon are called mild steels; those with about 0.45% carbon are medium steels; and
those with 0.60% to 2% carbon are high-carbon steels. Within this range, the greater the carbon content, the
greater the tensile strength of the steel. The hardness of steel may be substantially increased by heating the
metal until it is red hot and then quickly cooling it, a process known as quench hardening. An important
component of many steels is cementite, a carbon-iron compound. Mild steels are ductile and are fabricated
into sheets, wire, or pipe; the harder medium steels are used to make structural steel. High-carbon steels,
which are extremely hard and brittle, are used in tools and cutting instruments.

The addition of other materials in alloys (for example, manganese or silicon) also increases the hardness of
steel. The inclusion of tungsten permits high-speed drills and cutting tools to remain hard even when used at
high temperatures. The inclusion of chromium and nickel improves the corrosion resistance of the steel and,
within certain limits of composition, is called stainless steel. A common stainless steel contains 0.15% carbon,
18% chromium, and 8% nickel and is used in cooking utensils and food-processing equipment. The inclusion
of silicon, ranging from 1 to 5%, results in an alloy that is hard and highly magnetic. An alloy with cobalt is used
for permanent magnets.


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Page 44 of 180.

THE SIMULATION

Computer simulations of defect energies were run for both vacancies in BCC and FCC iron as well as free
surface energy for BCC iron.


Parameters for the simulations included the following facts about iron:
FCC: lattice parameter = 3.515Å, cohesive energy = 4.196eV
BCC: lattice parameter = 2.87Å, cohesive energy = 4.28eV

THE RESULTS


Figure 1 : Vacancy in a BCC crystal lattice.
For visualization purposes, the lattice atoms (arbitrarily designated so) are red and connected while the body
centered atoms are yellow. The vacancy is "located" within the inner red cube.
The BCC iron vacancy simulation resulted in a defect energy of 5.988eV.

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Page 45 of 180.

Figure 2 : Vacancy in a FCC crystal lattice.

Figure 3 : Vacancy in a FCC crystal lattice.
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Figure 4 : Vacancy in a FCC crystal lattice.
The above three figures show the simulation of a defect in FCC iron. Figure 2 is included for the benefit of the
reader. It is not "spiffed up," but rather shows the size and complexity of the simulation. The vacancy is the
irregularity toward the center of the figure. For visualization purposes, both Figure 3 (ortho projection) and
Figure 4 (perspective projection) show diagonals of all lattice faces. These are the "nearest neighbor" bonds.
The lattice face that "contains" the vacancy (a "face" atom) is emphasized by the yellow color of its face's
corners.
The FCC iron vacancy simulation resulted in a defect energy of 5.857eV.

The study of steels is important because steels represent by far the most widely used metallic materials,
primarily due to the fact that they can be manufactured relatively cheaply in large quantities to very precise
specifications. They also provide an extensive range of mechanical properties from moderate strength levels
(200-300MPa) with excellent ductility and toughness, to very high strengths (2000 MPa) with adequate ductility.
It is, therefore, not surprising that irons and steels comprise well over 80% by weight of the alloys in general
industrial use.

Steels form perhaps the most complex group of alloys in common use. Therefore, in studying them it is useful
to consider the behavior of pure iron first, then iron-carbon alloys, and finally examine the many complexities
which arise when further alloying additions are made.

Pure iron is not an easy material to produce. However, it has recently been made with a total impurity content
not exceeding 60 ppm (parts per million), of which 10 ppm is accounted for by non-metallic impurities such as
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Page 47 of 180.
carbon, oxygen, sulphur, phosphorus, while 50 ppm represents the metallic impurities. Iron of this purity is
extremely weak: the resolved shear stress of a single crystal at room temperature can be as low as 10 MPa,
while the yield stress of a polycrystalline sample at the same temperature can be well below 150 MPa.
The phase transformation: α- and γ- iron




BCC α-iron
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Page 48 of 180.

BCC α- iron

FCC γ- iron

Pure iron exists in two crystal forms, one body-centred cubic (bcc) (α-iron, ferrite) which remains stable from
low temperatures up to 910°C (the A3 point), when it transforms to a face-centred cubic (fcc) form (γ-iron,
austenite). The γ-iron on remains stable until 1390°C, the A4 point, when it reverts to bcc form, (now δ-iron)
which remains stable up to the melting point of 1536°C.

The detailed geometry of unit cells of α- and γ-iron crystals is particularly relevant to, for example, the solubility
in the two phases of non-metallic elements such as carbon and nitrogen, the diffusivity of alloying elements at
elevated temperatures, and the general behavior on plastic deformation.

The bcc structure of α-iron is more loosely packed than that of fcc γ-iron. The largest cavities in the bcc
structure are the tetrahedral holes existing between two edge and two central atoms in the structure, which
together form a tetrahedron.

It is interesting that the fcc structure, although more closely-packed, has larger holes than the bcc-structure.
These holes are at the centers of the cube edges, and are surrounded by six atoms in the form of an octagon,
so they are referred to as octahedral holes.

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Location of octahedral holes (left) and tetrahedral holes (right) relative to lattice spheres in face-centered cubic unit cell.
Note: The holes are gray and the lattice spheres are light blue in the unit cells above.

The α↔γ transformation in pure iron occurs very rapidly, so it is impossible to retain the high-temperature fcc
form at room temperature. Rapid quenching can substantially alter the morphology of the resulting α-iron, but it
still retains its bcc structure.

Carbon and nitrogen in solution in α- and γ- iron
The addition of carbon to iron is sufficient to form a steel. However, steel is a generic term which covers a very
large range of complex compositions. The presence of even a small concentration of carbon, e.g. 0.1-0.2
weight per cent (wt%); approximately 0.5-1.0 atomic per cent, has a great strengthening effect on iron, a fact
known to smiths over 2500 years ago since iron heated in a charcoal fire can readily absorb carbon by solid
state diffusion. However, the detailed processes by which the absorption of carbon into iron converts a
relatively soft metal into a very strong and often tough alloy have only recently been fully explored.
The atomic sizes of carbon and nitrogen are sufficiently small relative to that of iron to allow these elements to
enter the α- iron and &gamma- iron lattices as interstitial solute atoms. In contrast, the metallic alloying
elements such as manganese, nickel and chromium have much larger atoms, i.e. nearer in size to those of iron,
and consequently they enter into substitutional solid solution.

However, comparison of the atomic sizes of C and N with the sizes of the available interstices makes it clear
that some lattice distortion must take place when these atoms enter the iron lattice. Indeed, it is found that C
and N in α-iron occupy not the larger tetrahedral holes, but the octahedral interstices which are more favorably
placed for the relief of strain, which occurs by movement of two nearest neighbor iron atoms. In the case of
tetrahedral interstices, four iron atoms are of nearest-neighbor status and the displacement of these would
require more strain energy. Consequently these interstices are not preferred sites for carbon and nitrogen
atoms.

The solubility of both C and N in austenite should be greater than in ferrite, because of the larger interstices
available. It is, therefore, reasonable to expect that during simple heat treatments, excess carbon and nitrogen
will be precipitated. This could happen in heat treatments involving quenching from the γ state, or even after
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Page 50 of 180.
treatments entirely within the α field, where the solubility of C varies by nearly three orders of magnitude
between 720°C and 20°C.

Precipitation of carbon and nitrogen from α-iron. α-iron containing about 0.02 wt % C is substantially
supersaturated with carbon if, after being held at 700°C, it is quenched to room temperature. This
supersaturated solid solution is not stable, even at room temperature, because of the ease with which carbon
can diffuse in α-iron. Consequently, in the range 20-300°C, carbon is precipitated as iron carbide. This process
has been followed by measurement of changes in physical properties such as electrical resistivity, internal
friction, and by direct observation or the structural changes in the electron microscope.

The process of ageing is a two-stage one. The first stage takes place at temperatures up to 200°C and
involves the formation or a transitional iron carbide phase (ε) with a close-packed hexagonal structure which is
often difficult to identify, although its morphology and crystallography have been established. It forms as
platelets on {100}α planes, apparently homogenously in the α-iron matrix, but at higher ageing temperatures
(150-200°C) nucleation occurs preferentially on dislocations. The composition is between Fe2.4C and Fe3C.

Ageing at 200°C and above leads to the second stage of ageing in which orthorhombic cementite Fe3C is
formed as platelets on {110}α. Often the platelets grow on several {110} planes from a common centre giving
rise to structures which appear dendritic in character. The transition from ε-iron carbide to cementite is difficult
to study, but it appears to occur by nucleation of cementite at the ε-carbide/α interlaces, followed by re-solution
of the metastable ε-carbide precipitate.

The maximum solubility of nitrogen in ferrite is 0.10 wt %, so a greater volume fraction of nitride precipitate can
be obtained. The process is again two-stage with a be tetragonal α" phase, Fe16N2, as the intermediate
precipitate, forming as discs on {100}α, matrix planes both homogeneously and on dislocations. Above about
200°C, this transitional nitride is replaced by the ordered fcc γ’, Fe4N.

The ageing of α-iron quenched from a high temperature in the α-range is usually referred to as quench ageing,
and there is substantial evidence to show that the process can cause considerable strengthening, even in
relatively pure iron. In commercial low carbon steels, nitrogen is usually combined with aluminium, or present
in too low concentration to make a substantial contribution to quench ageing, with the result that the major
effect is due to carbon. This behavior should be compared with that of strain ageing.

Some practical aspects. The very rapid diffusivity of carbon and nitrogen in iron compared with that of the
metallic alloying elements is exploited in the processes of carburizing and nitriding.

Carburizing can be carried out by heating a low carbon steel in contact with carbon to the austenitic range, e.g.
1000°C, where the carbon solubility, c1, is substantial. The result is a carbon gradient in the steel, from c1 at
the surface in contact with the carbon, to c at a depth.

The diffusion coefficient D of carbon in iron actually varies with carbon content, so the above relationship is not
rigorously obeyed. Carburizing, whether carried out using carbon, or more efficiently using a carburizing gas
(gas carburizing), provides a high carbon surface on a steel, which, after appropriate heat treatment, is strong
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Page 51 of 180.
and wear resistant.

Nitriding is normally carried out in an atmosphere of ammonia, but at a lower temperature (500-550°C) than
carburizing, consequently the reaction occurs in the ferrite phase, in which nitrogen has a substantially higher
solubility than carbon.

Nitriding steels usually contain chromium (≈1%), aluminum (≈1%), vanadium or molybdenum (≈0.2%), which
are nitride-forming elements, and which contribute to the very great hardness of the surface layer produced.




http://www.msm.cam.ac.uk/doitpoms/tlplib/dislocations/dislocations_in_2D.php
http://www.ndt-ed.org/EducationResources/CommunityCollege/Materials/Introduction/introduction.htm
http://www.msm.cam.ac.uk/doitpoms/tlplib/solid-solutions/index.php

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Page 52 of 180.

Precipitation Hardening


Theory

The primary species of precipitation strengthening are second phase particles. These particles impede the
movement of dislocations throughout the lattice. You can determine whether or not second phase particles will
precipitate into solution from the solidus line on the phase diagram for the particles. Physically, this
strengthening effect can be attributed both to size and modulus effects, and to interfacial or surface energy.
The presence of second phase particles often causes lattice distortions. These lattice distortions result when
the precipitate particles differ in size from the host atoms. Smaller precipitate particles in a host lattice leads to
a tensile stress, whereas larger precipitate particles leads to a compressive stress. Dislocation defects also
create a stress field. Above the dislocation there is a compressive stress and below there is a tensile stress.
Consequently, there is a negative interaction energy between a dislocation and a precipitate that each
respectively cause a compressive and a tensile stress or vice versa. In other words, the dislocation will be
attracted to the precipitate. In addition, there is a positive interaction energy between a dislocation and a
precipitate that have the same type of stress field. This means that the dislocation will be repulsed by the
precipitate.
Precipitate particles also serve by locally changing the stiffness of a material. Dislocations are repulsed by
regions of higher stiffness. Conversely, if the precipitate causes the material to be locally more compliant, then
the dislocation will be attracted to that region.
Furthermore, a dislocation may cut through a precipitate particle. This interaction causes an increase in the
surface area of the particle. The area created is

where, r is the radius of the particle and b is the magnitude of the burgers vector. The resulting increase in
surface energy is

where is the surface energy. The dislocation can also bow around a precipitate particle.
Governing Equations
There are two equations to describe the two mechanisms for precipitation hardening:
Dislocations cutting through particles:
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where τ is material strength, r is the second phase particle radius, γ is the surface energy, b is the magnitude of
the Burgers vector, and L is the spacing between pinning points. This governing equation shows that the
strength is proportional to r, the radius of the precipitate particles. This means that it is easier for dislocations to
cut through a material with smaller second phase particles (small r). As the size of the second phase particles
increases, the particles impede dislocation movement and it becomes increasingly difficult for the particles to
cut through the material. In other words, the strength of a material increases with increasing r.
Dislocations bowing around particle:

where τ is the material strength, G is the shear modulus, b is the magnitude of the Burgers vector, L is the
distance between pinning points, and r is the second phase particle radius. This governing equation shows that
for dislocation bowing the strength is inversely proportional to the second phase particle radius r. Dislocation
bowing is more likely to occur when there are large particles present in the material.
These governing equations show that the precipitation hardening mechanism depends on the size of the
precipitate particles. At small r, cutting will be the dominant strengthening mechanism, while at large r, bowing
will be the dominant strengthening mechanism.

Looking at the plot of both equations, it is clear that there is a critical radius at which max strengthening occurs.
This critical radius is typically 5-30 nm.

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Some precipitation hardening materials
• 2000-series aluminum alloys (important examples: 2024 and 2019)
• 6000-series aluminum alloys
• 7000-series aluminum alloys (important examples: 7075 and 7475)
• 17-4PH stainless steel (UNS S17400)
• Maraging steel
• Inconel 718
• Alloy X-750
• Rene 41
• Waspaloy


Because precipitation strengthening is generally associated with a reduction in toughness, grain refinement is
often used in conjunction with precipitation strengthening to improve toughness.
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In most binary systems, alloying above a concentration given by the phase diagram will cause the formation of
a second phase. A second phase can also be created by mechanical or thermal treatments. The particles that
compose the second phase precipitates act as pinning points in a similar manner to solutes, though the
particles are not necessarily single atoms.
The dislocations in a material can interact with the precipitate atoms in one of two ways (see Figure 2). If the
precipitate atoms are small, the dislocations would cut through them. As a result, new surfaces (b in Figure 2)
of the particle would get exposed to the matrix and the particle/matrix interfacial energy would increase. For
larger precipitate particles, looping or bowing of the dislocations would occur which results in dislocations
getting longer. Hence, at a critical radius of about 5nm, dislocations will preferably cut across the obstacle
while for a radius of 30nm, the dislocations will readily bow or loop to overcome the obstacle.




Most precipitates in steels are relatively large (compared to GP zones in Al-Cu alloys for example) and strong
so dislocations have to travel between them rather than cut through them. This is called Orowan bowing. The
effectiveness of the precipitates in the steel depend on their composition (as this controls their thermodynamic
stability), size, volume fraction and distribution.
Slowly increase the applied force on the dislocation by holding the button down and see how a dislocation
bows around precipitates of different sizes and spacing. Plot a graph of precipitate bowing stress v average
separation.
Control of the precipitate type, size and distribution can be achieved in plate products using controlled
reheating, rolling and cooling schedules and careful alloying additions. The typical alloying additions that are
used to generate precipitate strengthening are Ti, V, Nb and Al. These additions can be made individually but
more commonly are made in combination depending on the requirements of strength, toughness etc. from the
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customer. The reason that these additions are used is that their precipitates (carbides and nitrides) have high
thermodynamic stability at elevated temperatures which means they also give rise to grain refinement during
processing in addition to strengthening at room temperature.

Alloying additions of fine precipitate forming elements can be used to refine the grain size of a steel. A fine
precipitate distribution in a steel will restrict the growth of austenite grains at high temperature and will retard
recrystallisation of deformed austenite grains. If the combination of precipitates and rolling schedule is used
then a 'pancake' structure of deformed austenite grains is created during rolling. These deformed grains
provide many nucleation sites for subsequent ferrite formation resulting in a fine grained ferritic structure in the
final steel product. The choice of alloying elements is important as the precipitates must be stable at the high
temperatures of processing in order to pin the grain boundaries. The typical alloying additions used in High
Strength Low Alloy steels (HSLA) are Nb, Al, Ti and / or V. They can be added in isolation or in combination
with one another.

Using the diagram above which alloying element gives you the most thermodynamically stable precipitate at
1150°C?
Ans: TiN
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An example of how alloying additions made in combination affect the strength (and toughness) is given below
for Al and V additions to a C-Mn ferrite + pearlite steel. The formation of AlN particles causes grain refinement
on heat treatment and some strengthening and the VC particles provided strengthening. Note that the
toughness decreases as the strength increases except for the strengthening effect of grain refinement which is
also beneficial to toughness.

ƒ Nb is used as a microalloying addition to control grain size and provide some precipitation strengthening.
ƒ V is used to provide precipitation strengthening. The strengthening that is obtained by V precipitates will
depend upon their size but a guideline is that for every 0.1 wt% V addition an increase of 50 - 60 MPa is
seen in strength


Precipitate hardening of stainless steel grades.
http://www.smihq.org/public/publications/past_articles/jan06_zubek.pdf
17-4PH precipitate hardened martensitic stainless steel.
http://www.sandmeyersteel.com/17-4PH.html
History of precipitate hardening.
http://nvl.nist.gov/pub/nistpubs/sp958-lide/014-015.pdf




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Chapter Two: The Effects of Alloying Elements on Iron-Carbon Alloys

Introduction:

Contributing factors to strength of steel.

The main contributions to the strength of steel come from:

ƒ Effect of grain size.
ƒ Effect of microstructure.
ƒ Effect of solid solution strengthening.
ƒ Effect of precipitates.
ƒ Effect of dislocations.
These factors are controlled by the chemistry of the steel and the processing route used to produce the final
component. All of these aspects need to be taken into account when selecting or designing steel for a given
application.
The processing routes include:
ƒ Alloying.
ƒ Thermal heat treatment.
ƒ Mechanical straining and deformation.
ƒ Thermo-mechanical in combination e.g. TMCP steels.
ƒ Age hardening.
ƒ Mechanical alloying or dispersion hardening.
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Effect of High Heat input on CTOD Property of the Thick Steel Plate for Offshore Engineering
Heat treatment of Steels
Steel forming and heat treating handbook
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Ways of improving the strength of alloy steels are:

The solid-solution hardening of carbon has a major effect on the strength of martensite, but ductility can only
be obtained at low carbon levels. Although alloying elements affect hardenability, they have a minor effect on
hardness except to reduce it at high carbon levels by causing austenite to be retained.
1. Grain refinement:
which increases strength and ductility. This can be developed by severely curtailing the time after the
cessation of forging at some low temperature of austenite stability or by rapid heating, coupled with a
short austenitising period. Fine grain is produced in 9% Ni steel by tempering fine lath martensite.

2. Precipitation hardening by carbide, nitride or intermetallic compounds:

ƒ By secondary hardening, e.g. 12% Cr steel with additions.
ƒ Age hardening a low carbon Fe-Ni lath martensite supersaturated with substitutional elements, e.g.
maraging.
ƒ Age hardening of austenite, e.g. stainless steels. Phosphorus and titanium are common additions.
Stacking faults are often associated with fine carbide precipitates, and strength can be raised by
increasing the number of stacking faults (i.e. lower fault energy).
ƒ Controlled transformation 18/8 austenite steels in which transformation to martensite is induced by
refrigeration or by strain.

3. Thermomechanical treatments
which may be classified into three main groups:
ƒ Deformation of austenite prior to the transformation.
Ausforming consists of steel deforming in a metastable austenitic condition between Ac1 and Ms (e.g.
500 called LT) followed by transformation to martensite and light tempering (Fig. 1). This results in
increased dislocation density in the martensite and a finer carbon precipitation on tempering.
Strengths up to 1800 MPa can be obtained without impairing the ductility (~6 % deformation). Steels
must possess a TTT-curve with a large bay of stable austenite, e.g. 826 M40. Typical application is
for leaf springs.


Figure 1. Methods of thermomechanical treatment
Deformation of stable austenite just above Ac3 before cooling (called HT). The properties are
somewhat inferior to those produced by ausforming.
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Deformation induced transformation originally used in Hadfield 13% Mn steel, but can be adapted to
metastable austenitic stainless steels. The fully austenitic steel is severely warm-worked above the
lowest temperature at which martensite is produced during the straining. The distinctive property is
the high rate of straining hardening, which increases ductility.

ƒ Deformation of austenite during the transformation
Isoforming is the deformation of a steel (e.g. 1% Cr) during the isothermal transformation to pearlite,
which refines the structure and improves fracture toughness (Fig. 1). A somewhat similar
thermomechanical process can be used in the bainitic region, producing bainite and martensite.
Zerolling consists in forming martensite by deformation at subzero temperatures to strengthen 18/8
austenitic steels. The amount of martensite is influenced by alloy composition and increased with
deformation and lowering of the temperature.

ƒ Deformation after the transformation of austenite
Marforming consists of deforming the maraging steel in the soft martensitic condition, generally cold.
There is a pronounced increase in strength of the subsequent maraged product. With other steels,
considerable increases in strength can be obtained by straining martensite (~3 %) either in the
untempered or tempered condition. A strengthening effect also occurs on re-tempering, probably due
to the resolution and reprecipitation of the carbides in a more finely dispersed form.
Strain tempering and dynamic strain ageing. Both processes involve about 5% deformation at the
room temperature between two stages of tempering -- strain tempering -- while in dynamic strain
ageing deformation is concurrent with tempering.

4. Solid solution Hardening:
For ferrite and pearlite steels relationships between yield and tensile strength and various compositional
and microstructural factors have been developed. These are useful in that they show general
characteristics, although they are unable to incorporate all factors that influence strength in modern steels,
for example precipitation strengthening. Examples of these relationships are given below:

YS (MPa) = 53.9 + 32.3 Mn + 83.2 Si + 354 N
f
+ 17.4 d
-1/2

UTS (MPa) = 294 + 27.7 Mn + 83.2 Si + 3.85 pearlite % + 7.7 d
-1/2

Alloying addition in wt%, d is the ferrite grain size in mm, N
f
is the free nitrogen content
ASTM
Designation No.
Size Range,
Inclusive, in.
Minimum
Proof
Strength,
kpsi
Minimum
Tensile
Strength,
kpsi
Minimum
Yield
Strength,
kpsi
Material
A307 .25-1.5 33 60 36 Low Carbon
A325, Type 1 0.5-1.0, 1.125-1.4 85, 74 120, 105 92, 81 Medium Carbon, Q&T
A325, Type 2 0.5-1.0, 1.125-1.5 85, 75 120, 106 92, 82
Low Carbon Martensite,
Q&T
A325, Type 3 0.5-1.0, 1.125-1.6 85, 76 120, 107 92, 83 Weathering Steel, Q&T
A354,
Alloy Steel, Q&T
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Grade BC
A354, Grade BD 0.25-4.0 120 150 130 Alloy Steel, Q&T
A449
0.25-1.0,
1.125-1.5,
1.75-3.0
85, 74, 55 120, 105, 90 92, 81, 58 Medium Carbon, Q&T
A490, Type 1 0.5-1.5 120 Alloy Steel, Q&T
A490, Type 3 Weathering Steel, Q&T

The microstructure of steel has a significant effect on the strength of steel. For steel with a certain
composition the microstructure can be altered through varying the processing route used. For example
for strip steels the coiling temperature can be controlled to give varying microstructures in the final coil
with varying properties.
In this example, different yield strengths can be achieved for a fixed composition by obtaining different
microstructures.
Changing the amount of second phase in a predominantly ferritic microstructure has a pronounced
effect on the strength of the steel. This microstructural change can be achieved through control of
composition and processing as mentioned earlier. For structural steels produced as plate and sections
with a ferrite + pearlite microstructure relatively small changes in the amount of pearlite and ferrite at
low levels (~5-10%) have a relatively small effect on the strength level, especially the yield strength as
the surrounding ferrite yields first anyway.
The presence of dislocation networks produced through work hardening can result in very high levels of
strength, however, it reduces toughness and ductility so is used only for certain steel products. Work
hardening is not used to any extent in plate and section steel products but is used in some strip and
engineering steel products. For example:

Strip products
Some strip grades that do not require a high level of formability but an increased strength level are
supplied with a degree of work hardening. This work hardening is achieved through controlled cold
rolling passes after any annealing process (annealing removes the dislocation structure by recovery or
recrystallisation). The level of work hardening introduced is determined by the strain during the cold roll
passes (i.e. the thickness reduction per pass) and controlled to give the strength levels required. Work
hardening, and hence strengthening, can also occur during fabrication, for example during press
forming, bending, drawing etc.

High carbon steel products
For example steel wire is often supplied in a work hardened condition as the dislocation networks
provide much of the strengthening. High strength steel wire is used in suspension cables, tyre cords,
pre-stressed wire and wires can have yield strength up to 5000 MPa (lower strength values are usually
seen for the applications mentioned). The wire is cold drawn from hot rolled to 90% reduction which
produces a heavily worked structure
Typical 'mild' steels have a small carbon content, usually under 0.2%. Increasing the carbon content
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hardens the steel and its ability to take and hold an edge but at the expense of toughness. Adding other
alloying elements can alter these properties, though usually at the expense of increased cost and
manufacturability. The main alloying elements and their effects are described in next section. Carbon
steels usually contain less than 1 to 2% carbon and small quantities of manganese, copper, silicon,
sulfur, and phosphorus. Alloy steels are carbon steel with other metals added specifically to improve the
properties of the steel significantly. Stainless steel is considered a separate group. Plain carbon steel
is produced with a wide range of mechanical properties with comparatively low cost. To extend the
range of properties of steel, alloys have been developed.

The benefits of alloying resulting include

• The maximum UTS is increased.
• Thick sections steels are available with high hardness throughout the section.
• More controllable quenching with minimum risk of shape distortion or cracking.
• Improved impact resistance at high temperature range.
• Improved corrosion resistance.
• Improved high temperature performance.
The principle elements that are used in producing alloy steel include nickel, chromium, molydenenum,
manganese, silicon and vanadium. Cobalt, copper and lead are also used as alloying elements.
Steels for special applications EF420 Lecture 7:


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Cast Irons EF420 Lecture 9:

Ferrous Alloys EF420 Lecture 12:

http://www.slideshare.net/charliechong/askeland-phule-notes-ch12-printable-presentation


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Effects of thermomechanical treatment on microstructure and mechanical properties of T91 steel

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Alloying:

Effect of alloying elements

ƒ Elements may encourage formation of graphite from the carbide. Only a small proportion of these
elements can be added to the steel before graphite forms destroying the properties of the steel, unless
elements are added to counteract the effect. Elements which encourage the formation of graphite include
silicon, cobalt, aluminium and nickel.
ƒ Alloying elements may go into solid solution in the iron, enhancing the strength. Elements which go into
solid solution include silicon, molybdenum, chromium, nickel and magnesium.
ƒ Hard carbides (cementite) associated with iron and carbon may be formed with alloying elements.
Elements which tend to form carbides include chromium, tungsten, titanium, columbium, vanadium,
molybdenum and manganese.
ƒ Elements which stabilize austenite include manganese, nickel, cobalt and copper. These increase the
range over which austenite is stable e.g. by lowering the eutectoid temperature, and this retards the
separation or carbides.
ƒ Elements which tend to stabilize ferrite include chromium, tungsten, molybdenum, vanadium and
silicon. They reduce the amount of carbon soluble in the austenite and thus increase the volume of free
carbide in the steel at a given carbon content. The effectively reduce the austenite ( γ ) phase by raising
the eutectoid temperature and lowering the peritectic temperature. Intermediate compounds with iron may
be formed e.g. FeCr. Alloying elements may adjust the characteristics such as eutectoid content,
quenching rate which produces bainite or martensite.


Relative effect of alloying elements

The combined effect of alloying elements results from many complex interactions resulting from the processing
history, the number and quantities of constituents, the heat treatments, the section shape etc. Some basic
rules can be identified.
ƒ Nickel has reduced carbide forming tendency than iron and dissolves in α ferrite.
ƒ Silicon combines with oxygen to form nonmetallic inclusions or dissolves in the ferrite.
ƒ Most of the manganese in alloy steels dissolves in the α ferrite. Any manganese that form carbides result
in (Fe,Mn)3C.
ƒ Chromium spreads between the ferrite and carbide phases the spread depending on the amount of
carbon and other carbide generating elements present.
ƒ Tungsten and molybdenum form carbides if sufficient carbon is present which has not already formed
carbides with other stronger carbide forming elements.
ƒ Vanadium, titanium, and Colombian are strong carbide forming elements and are present in steel as
carbides.
ƒ Aluminium combines with oxygen and nitrogen to form Al2O an AlN

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Characteristics of alloying

Alloying Additions to Steel

Steels are among the most commonly used alloys. The complexity of steel alloys is fairly significant. Not all
effects of the varying elements are included. The following text gives an overview of some of the effects of
various alloying elements. Additional research should be performed prior to making any design or engineering
conclusions.


Element Influence Uses
Carbon
Hardness - Strength - Wear
Most important alloying element. Is essential to
the formation of cementite and other carbides,
bainite and iron-carbon martensite. Within limits
increasing the carbon content increases the
strength and hardness of a steel while reducing its
toughness and ductility.
Added to construction steels to
increase strength, hardness and
hardenability.
Aluminum Deoxidation - Ease of Nitriding
Boron Hardenability
Copper Corrosion Resistance - Strength
Lead Machinability
Phosphorus Strength
Silicon
Tellurium Machinabilty
Nickel
Toughness - Strength - Hardenability
Stabilises gamma phase by raising A
4
and
lowering A
3
. Refines grains in steels and some
non-ferrous alloys. Strengthens ferrite by solid
solution. Unfortunatly is a powerful graphitiser.
Can take into solid solution larger proportions of
important elements such as chromium,
molybdenum and tungsten than can iron.
Used up to help refine grain size. Used
in large amounts in stainless and
heat-resisting steels.
Nickel based alloys can offer corrosion
resistance in more aggressive
environments and nickel is used as the
basis of complex superalloys for high
temperature service.
Manganese
Strength - Hardenability - More Response To Heat
Treatment
Deoxidises the melt. Greatly increases the
hadenability of steels. Stabilises gamma phase.
Forms stable carbides.
High manganese (Hadfield) steel
contains 12.5% Mn and is austenitic
but hardens on abrasion.
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Silicon
Carbide former.
Hardenability De-oxidizes melt. Helps casting
fluidity. Improves oxidation resistance at higher
temperatures.
Up to 0.3% in steels for sand casting,
up to 1% in heat resisting steels.
Chromium
Corrosion Resistance - Strength
Stabilises alpha phase by raising A
3
and
depressing A
4
. Forms hard stable carbides.
Strengthens ferrite by solid solution. In amounts
above 13% it imparts stainless properties.
Unfortunately increases grain growth.
Small amounts in constructional and
tool steels. About 1.5% in ball and
roller bearings. Larger amounts in
Stainless and heat-resisting steels.
Molybdenum
High Temperature Strength - Hardenability
Strong carbide-stabilising influence. Raises high
temperature creep strength of some alloys. Slows
tempering response.
When added to stainless steels it greatly improves
the pitting and crevice corrosion resistance. There
are limits to the proportion that can be taken into
an iron based matrix. However up to almost 30%
can be incorporated into nickel based alloys which
provides excellent corrosion resistance in many
aqueous environments.
Reduces 'temper brittleness' in
nickel-chromium steels. Increases
red-hardness of tool steels. Now used
to replace some tungsten in
high-speed steels.
Vanadium
Fine Grain - Toughness
Strong carbide forming tendency. Stabilises
martensite and increases hardenability. Restrains
grain growth. Improves resistance to softening at
elevated temperatures after hardening.
Used to retain high temperature
hardness, e.g. in dies for hot-forging
and die casting dies. Increasingly used
in high speed steels.
Tungsten
Stabilises alpha phase and forms stable, very
hard carbides, which improves creep resistance
and renders transformations very sluggish, hence
hardened steels resist tempering influences.
Used in high-speed steels and other
tool and die steels, particularly those
for use at high temperatures.
Used in a few stainless steels, in
combination with molybdenum. to
improve pitting and crevice corrosion
resistance. It is also used in some high
temperature nickel based alloys and in
some high temperature austenitic
stainless steels.
Cobalt
Hardness - Wear
Has similar corrosion resistance to that of Nickel,
but higher cost means that it is not normally used
for such applications.
Provides matrix - strengthening characteristics to
stainless and nickel based alloys designed for
high temperature applications.
Used in super high speed steels and
maraging steels, permanent magnet
steels and alloys.
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Slows the transformation of martensite, hence
increases 'red hardness' which is useful in tool
steels.
Niobium
Elimination Of Carbide Precipitation
In low alloy steels it acts as a carbide former and
improves creep resistance.
In stainless steels it combines with carbon,
stabilising the steel and reducing the susceptibility
to intergranular corrosion
Used to stabilize stainless steels.
Titanium
Elimination Of Carbide Precipitation
In stainless steels combines with excess carbon
reducing the risk of intergranular corrosion.
Used in stabilized stainless steels.
In nickel based alloys it is used with
aluminium to promote age hardening.

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Effects of Alloying Elements on the Microstructures and Mechanical on ductile cast irons
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Carbon

Carbon has a major effect on steel properties. Carbon is the primary hardening element in steel. Hardness
and tensile strength increases as carbon content increases up to about 0.85% C as shown in the figure
above. Ductility and weldability decrease with increasing carbon.
Carbon is essential in steels which have to be hardened by quenching and for example, in austenitic
manganese steel which is required to have high resistance to wear. The maximum hardness obtainable in any
carbon steel is a function of the carbon content which may vary up to about 2% according to the purpose for
which the steel is to be used. It occurs in varying forms according to the percentage present, and the heat
treatment to which the steel has been submitted. (See allotropy and transformation range). Cast irons usually
contain from about 1.8% to 4.5% carbon, present either as free carbon (graphite) and/or combined carbon
(cementite), the varying distribution of the carbon between these two forms considerably influencing the
strength and hardness.
Carbon is a strong austenite former and strongly promotes an austenitic structure. It also substantially
increases the mechanical strength. Carbon reduces the resistance to intergranular corrosion. In ferritic
stainless steels carbon will strongly reduce both toughness and corrosion resistance. In the martensitic and
martensitic-austenitic steels carbon increases hardness and strength. In the martensitic steels an increase in
hardness and strength is generally accompanied by a decrease in toughness and in this way carbon reduces
the toughness of these steels.
Carbon: Present in all steels, it is the most important hardening element. Also increases the strength of the
steel. We usually want knife-grade steel to have >.5% carbon, which makes it "high-carbon" steel.
it has by far the greatest influence of any of the elements. Steel could not exist without carbon. Martensite,
along with banite gives steel a microstructure of hard, tough carbide. None of the other elements so
dramatically alter the strength and hardness as do small changes in carbon content. Carbon
iron crystalline structures have the widest number and variety known to exist in metallurgy. They also
combine with other elements to furnish steel with an assortment of iron alloy carbide systems.

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Manganese

Manganese fulfils a variety of functions in steel.

ƒ It is used as a deoxidizing agent in nearly all steels.
ƒ It forms manganese sulphide inclusions which in the ingot are spherical. In the absence of
manganese sulphur forms interdendritic films of iron sulphide causing brittleness at forging
temperature (hot shortness).
ƒ It effectively increases harden ability and up to 1.5% is added for this purpose. (d) In larger amounts
it is used to stabilize austenite, as in 14% manganese steel.

MANGANESE (Mn): Is normally present in all steel and functions as a deoxidizer. It also imparts strength
and responsiveness to heat treatment. It is usually present in quantities of 0.5 to 2.0 percent. Range 0.3% to
1.5% always present in steels to reduce the negative effects of impurities carried out forward from the
production process e.g. sulphur embrittlement. It promotes the formation of stable carbides in
quenched-hardened steels. Alloys containing manganese are pearlitic. Up to 1% acts as hardening agent and
from 1% to 2% improves strength and toughness. Alloys containing more than 5% are non-magnetic. Alloys
containing large proportions of up to 12.5% manganese have the property that they spontaneously form hard
skins when subject to abrasion. (Self-hardening)

All commercial steels contain 0.3-0.8% manganese, to reduce oxides and to counteract the harmful influence
of iron sulfide. Any manganese in excess of these requirements partially dissolves in the iron and partly forms
Mn
3
C which occurs with the Fe
3
C. There is a tendency nowadays to increase the manganese content and
reduce the carbon content in order to get steel with an equal tensile strength but improved ductility
If the manganese is increased above 1,8% the steel tends to become air hardened, with resultant impairing of
the ductility. Up to this quantity, manganese has a beneficial effect on the mechanical properties of oil
hardened and tempered 0.4% carbon steel. The manganese content is also increased in certain alloy steels,
with a reduction or elimination of expensive nickel, in order to reduce costs. Steels with 0.3-0.4% carbon,
1,3-1,6% manganese and 0.3% molybdenum have replaced 3% nickel steel for some purposes.

Non-shrinking tool steel contains up to 2% manganese, with 0.8-0.9% carbon. Steels with 5 to 12%
manganese are martensitic after slow cooling and have little commercial importance.

Hadfield`s manganese steel a specially steel which is austenitic and usually contains approximately 12%
Manganese. It is used in mining, earth- moving equipment and in railroad track work. . Hadfield`s manganese
steel contains 12 to 14% of manganese and 1,0% of carbon. It is characterized by a great resistance to wear
and is therefore used for railway points, rock drills and stone crushers. Austenite is completely retained by
quenching the steel from 1000°C, in which soft condition it is used, but abrasion raises the hardness of the
surface layer from 200 to 600 VPN (with no magnetic change), while the underlying material remains rough.
Annealing embrittles the steel by the formation of carbides at the grain boundaries. Nickel is added to
electrodes for welding manganese steel and 2% Mo sometimes added, with a prior carbide dispersion
treatment at 600°C, to minimize initial distortion and spreading.


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http://www.arema.org/eseries/scriptcontent/custom/e_arema/library/2005_Conference_Proceeding
s/00040.pdf

Manganese is generally beneficial to surface quality especially in resulfurized steels. Manganese contributes
to strength and hardness, but less than carbon. The increase in strength is dependent upon the carbon
content. Increasing the manganese content decreases ductility and weldability, but less than carbon.
Manganese has a significant effect on the hardenability of steel.
Manganese aids the grain structure, and contributes to hardenability, strength & wear resistance. Improves the
steel (e.g. deoxidizes) during the steel's manufacturing (hot working and rolling). Present in most cutlery steel
except for A-2, L-6 and CPM 420V. Manganese slightly increases the strength of ferrite, and also increases the
hardness penetration of steel in the quench by decreasing the critical quenching speed. This also makes the
steel more stable in the quench. Steels with manganese can be quenched in oil rather than water, and
therefore are less susceptible to cracking because of a reduction in the shock of quenching. Manganese is
present in most commercially made steels.

Manganese is generally used in stainless steels in order to improve hot ductility. Its effect on the
ferrite/austenite balance varies with temperature: at low temperature manganese is a austenite stabiliser but at
high temperatures it will stabilize ferrite. Manganese increases the solubility of nitrogen and is used to obtain
high nitrogen contents in austenitic steels.


Figure 1: Non-metallic inclusion in steel: oxides-dark gray and sulfides-light gray

Manganese is generally used in stainless steels in order to improve hot ductility. Its effect on the
ferrite/austenite balance varies with temperature: at low temperature manganese is a austenite stabiliser but at
high temperatures it will stabilise ferrite. Manganese increases the solubility of nitrogen and is used to obtain
high nitrogen contents in austenitic steels.

In general Manganese increases strength and hardness; forms carbide; increases hardenability; lowers the
transformation temperature range. When in sufficient quantity produces austenitic steel; always present in a
steel to some extent because it is used as a deoxidizer

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Figure 2: Typical duplex oxide–sulfide inclusion (particle A, B and C) and plate-like MnS (particle D) in conventional
continuous casting silicon steel.

SEM of an inclusion.



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Nickel

ƒ Increase Strength.
ƒ Improve Toughness.
ƒ Unable to increase Hardness
ƒ Ferrite Former.
NICKEL (Ni): Increases strength and toughness but is ineffective in increasing hardness. It is generally
added in amounts ranging from 1 percent to 4 percent. In some stainless steels it is sometimes as high as 20
percent. It is used for strength, corrosion resistance, and toughness, nickel increases the strength of ferrite,
therefore increasing the strength of the steel. It is used in low alloy steels to increase toughness and
hardenability. Nickel also tends to help reduce distortion and cracking during the quenching phase of heat
treatment.
Nickel is a ferrite strengthener. Nickel does not form carbides in steel. It remains in solution in
ferrite, strengthening and toughening the ferrite phase. Nickel increases the hardenability and impact strength
of steels. Range 0.2% to 5% Improves strength, toughness, and hardenability without seriously affecting the
ductility. It encourages grain refinement. Nickel and chromium together have opposing properties and are
used together to advantage in nickel-chrome steels. The resulting steels have their advantages combined
and their undesirable features cancel each other At 5% nickel provides high fatigue resistance. When alloyed
at higher proportions significant corrosion resistance results and at 27% a non magnetic stainless steel results.
The addition of nickel, in amounts up to 8% or 10 %, to low carbon steel, increases the tensile strength and
considerably raises the impact resistance. 9% nickel steels are useful at very low temperatures. In
engineering steels it is widely used, often with chromium and molybdenum. High nickel increases resistance
to corrosion, and in combination with chromium, is used in the austenitic corrosion-resisting steels. Certain
iron-nickel alloys have unique properties. 25% nickel steel is practically non-magnetic. Alloys with about 36%
nickel have very low coefficients of expansion, whilst with 50% to 78.5% nickel; alloys are obtained having
very high magnetic permeability in low fields. An alloy containing 29% nickel, 17% cobalt is used for sealing
with certain borosilicate glasses.
For stainless steel, the main reason for the nickel addition is to promote an austenitic structure. Nickel
generally increases ductility and toughness. It also reduces the corrosion rate and is thus advantageous in acid
environments. In precipitation hardening steels nickel is also used to form the intermetallic compounds that are
used to increase the strength.
Nickel and manganese are very similar in behavior and both lower the eutectoid temperature. This change
point on heating is lowered progressively with increase of nickel (approximately 10°C for 1% of nickel), but the
lowering of the change on cooling is greater and irregular. The temperature of this change (Ar
1
) is plotted for
different nickel contents for 0.2% carbon steels in Fig. 1, It will be seen that the curve takes a sudden plunge
round about 8% nickel. A steel with 12% nickel begins to transform below 300°C on cooling, but on reheating
the reverse change does not occur until about 650°C. Such steels are said to exhibit pronounced lag or
hysteresis and are called irreversible steels. This characteristic is made use of in maraging steels and 9% Ni
cryogenic steel.
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It Increases strength and toughness but is ineffective in increasing hardness. It is generally added in amounts
ranging from 1 percent to 4 percent. In some stainless steels it is sometimes as high as 20 percent.


Maraging steels are a class of high-strength steel with low carbon content and the use of
substitutional (as opposed to interstitial) elements to produce hardening from formation of nickel
martensites. The name maraging has resulted from the combination of
Martensite + Age hardening

Maraging steels contain 18% nickel, along with a amounts of molybdenum, cobalt, and titanium
and aluminium, and almost no carbon. These alloys can be strengthened significantly by a
precipitation reaction at a relatively low temperature. They can be formed and machined in the
solution-annealed condition but not without difficulty. Weldability is excellent. Fracture
toughness of the maraging steels is considerably higher than that of the conventional
high-strength steels. Maraging steels are hardened by a metallurgical reaction that does not
involve carbon. Maraging steels are strengthened by intermetallic compounds such as Ni
3
Ti
and Ni
3
Mo which precipitate at about 500°C. The carbon content provides no real benefit and is
kept low as possible in order to minimize the formation of titanium carbide which can adversely
affect mechanical properties. Toughness is superior to all low alloy carbon steels of similar
strength, particularly the low temperature toughness. These steels are easy to machine and
heat treat, so some cost savings result in component production to compensate for the high cost
of the steel. A high strength maraging steel (extrusion section MIL-S-46850 grade 300) can have
a 0.2% proof stress of 1930MPa and Ultimate Tensile strength of 2068 MPa with an elongation
of 4%

The addition of nickel acts similarly to increasing the rate of cooling of a carbon steel. Thus with a constant rate
of cooling the 5 to 8% nickel steels become troostitic; at 8 to 10% nickel, where the sudden drop appears, the
structure is martensitic, while above 24% nickel the critical point is depressed below room temperature and
austenite remains. The lines of demarcation are not so sharp as indicated by Fig. 1, but a gradual transition
occurs from one constituent to another.

Nickel
Strengthens steel; lowers its transformation temperature range; increases hardenability, and improves
resistance to fatigue. Strong graphite forming tendency; stabilizes austenite when in sufficient quantity.
Creates fine grains and gives good toughness.
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Figure1. Effect of nickel on change points and mechanical properties of 0.2% carbon steels cooled at a constant rate.

The mechanical properties change accordingly as shown in the lower part of Fig. 1. Steels with 0.5% nickel are
similar to carbon steel, but are stronger, on account of the finer pearlite formed and the presence of nickel in
solution in the ferrite. When 10% nickel is exceeded the steels have a high tensile strength, great hardness,
but are brittle, as shown by the Izod and elongation curves. When the nickel is sufficient to produce austenite
the steels become non-magnetic, ductile, tough and workable, with a drop in strength and elastic limit.

Carbon intensives the action of nickel and the change points shown in Fig. 1 will vary according to the carbon
content. The influences of carbon and nickel on the structure are shown in the small inset (Guillet) diagram in
Fig. 1, for one rate of cooling. Steels containing 2 to 5% nickel and about 0.1% carbon are used for case
hardening; those containing 0.25 to 0.40% carbons are used for crankshafts, axles and connecting rods.

The superior properties of low nickel steels are best brought out by quenching and tempering (550-650°C).
Since the Ac
3
point is lowered, a lower hardening temperature than for carbon steels is permissible and also a
wider range of hardening temperatures above Ac3 without excessive grain growth, which is hindered by the
slow rate of diffusion of the nickel. Martensitic nickel steels are not utilized and the austenitic alloys cannot
compete with similar manganese steels owing to the higher cost. Maraging steels have fulfilled a high tensile
requirement in aero and space fields. High nickel alloys are used for special purposes, owing to the marked
influence of nickel on the coefficient of expansion of the metal. With 36% nickel, 0.2% carbon, 0.5%
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manganese, the coefficient is practically zero between 0°C and 100°C. This alloy ages with time, but this can
be minimized by heating at 100°C for several days.

The alloy is called Inver and it is used extensively in clocks, tapes and wire measures, differential expansion
regulators, and in aluminum pistons with a split skirt in order to give an expansion approximating to that of cast
iron. A carbon-free alloy containing 78.5% nickel and 21.5% iron has a high permeability in small magnetic
fields.


Figure 6: Vertical section of Fe-Cr-C diagram for 0.1C wt%.


Figure 7: Schaeffler diagram for weld metals.
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Chromium

Chromium is commonly added to steel to increase corrosion resistance and oxidation resistance, to increase
hardenability, or to improve high-temperature strength. As a hardening element, Chromium is frequently used
with a toughening element such as nickel to produce superior mechanical properties. At higher temperatures,
chromium contributes increased strength. Chromium is strong carbide former. Complex chromium-iron
carbides go into solution in austenite slowly; therefore, sufficient heating time must be allowed for prior to
quenching.
It is added for wear resistance, hardenability, and (most importantly) for corrosion resistance. As with
manganese, chromium has a tendency to increase hardness penetration. When 5 percent chromium or more
is used in conjunction with manganese, the critical quenching speed is reduced to the point that the steel
becomes air hardening. Chromium can also increase the toughness of steel, as well as the wear resistance.

As an alloying element in steel, chromium increases the hardenability and in association with high carbon
gives resistance to abrasion and wear. 4%is present in high speed steel and up to 5% is present in hot die
steels. In Structural steels it may be present in amounts up to about 3 %. Simple chromium-carbon steels are
used for ball bearings having high elastic limit and high uniform hardness due to the uniform distribution of the
hard carbide particles, but for most structural purposes chromium is used in conjunction with up to 4 % nickel
and small amounts of molybdenum or vanadium. In heat-resisting steels, chromium is present in amounts up
to 30%, and it is an important element in many of the highly alloyed heat-resisting materials, whose iron
contents are so low that they cannot be regarded as steel. Chromium is also used as an alloying addition to
high duty cast irons.
This is the most important alloying element in stainless steels. It is this element that gives the stainless steels
their basic corrosion resistance. The corrosion resistance increases with increasing chromium content. It also
increases the resistance to oxidation at high temperatures. Chromium promotes a ferritic structure. Chromium
is unique in its effect on resistance to corrosion and scaling and is an essential constituent in all stainless
steels, e.g., stainless cutlery steels contain 12% to 14% chromium, whilst in steels of the austenitic
corrosion-resisting type, 18% chromium is associated with 8% nickel, and small amounts of other elements.
Steel with at least 13% chromium is deemed "stainless" steel. Despite the name, all steel can rust if not
maintained properly. Chromium can dissolve in either alpha- or gama-iron, but, in the presence of carbon, the
carbides formed are cementite (FeCr)
3
C in which chromium may rise to more than 15%; chromium carbides
(CrFe)
3
C
2
(CrFe)
7
C
3
(CrFe)
4
C, in which chromium may be replaced by a few per cent, by a maximum of 55%
and by 25% respectively. Stainless steels contain Cr
4
C. The pearlitic chromium steels with, say, 2% chromium
are extremely sensitive to rate of cooling and temperature of heating before quenching;
It increases the depth penetration of hardening and also the responsiveness to heat treatment. It is usually
added with nickel (Ni) for use in stainless steels. Most of the chromium (Cr) bearing alloys contain 0.50 to
1.50 percent chromium; some stainless steels contain as much as 20 percent or more. It can affect forging,
causing a tendency in the steel to crack.

For example:

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Temperature of Initial Heating, °C
Critical Hardening Rate
(Min. to cool from 836°C to 546°C)
836 3.5 S
1010 6.5 S
1200 13 S

The reason is that the chromium carbides are not readily dissolved in the austenite, but the amount increases
with increase of temperature. The effect of the dissolved chromium is to raise the critical points on heating (Ac)
and also on cooling (Ar) when the rate is slow. Faster rates of cooling quickly depress the Ar points with
consequent hardening of the steel. Chromium imparts a characteristic form of the upper portion of the
isothermal transformation curve.
The percentage of carbon in the pearlite is lowered. Hence the proportion of free cementite (hardest
constituent) is increased in high carbon steel and, when the steel is properly heat-treated, it occurs in the
spheroidised form which is more suitable when the steel is used for ball bearings. The pearlite is rendered fine.
When the chromium exceeds 1.1% in low-carbon steels an inert passive film is formed on the surface which
resists attack by oxidizing reagents. Still higher chromium contents are found in heat-resisting steel.

Chromium steels are easier to machine than nickel steels of similar tensile strength. The steels of higher
chromium contents are susceptible to temper brittleness if slowly cooled from the tempering temperature
through the range 550/450°C. These steels are also liable to form surface markings, generally referred to as
"chrome lines". The chrome steels are used wherever extreme hardness is required, such as in dies, ball
bearings, plates for safes, rolls, files and tools. High chromium content is also found in certain permanent
magnets.

Figure 2. Effect of alloying with chromium on the critical temperature of steel and austenite (g -iron) phase transformation
zone on the iron-iron carbide diagram.
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Nickel and chromium

Nickel steels are noted for their strength, ductility and toughness, while chromium steels are characterized by
their hardness and resistance to wear. The combination of nickel and chromium produces steels having all
these properties, some intensified, without the disadvantages associated with the simple alloys. The depth of
hardening is increased, and with 4,5% nickel, 1,25% chromium and 0.35% carbon the steel can be hardened
simply by cooling in air.
Low nickel-chromium steels with small carbon content are used for casehardening, while for most
constructional purposes the carbon content is 0.25-0.35%, and the steels are heat-treated to give the desired
properties. Considerable amounts of nickel and chromium are used in steel for resisting corrosion and
oxidation at elevated temperatures.
Embattlement. The effects of tempering a nickel-chromium steel are shown in Fig. 2, from which it will be
noticed that the Izod impact curve No. 1 reaches a dangerous minimum in the range 250-450°C in common
with many other steels. This is known as 350°C embattlement. Phosphorus and nitrogen have a significant
effect while other impurities (As, Sb, Sn) and manganese in larger quantity may also contribute to the
embattlement.

Figure 2. Effect of tempering on the mechanical properties of nickel-chromium steel, C 0.26, Ni 3, Cr 1,2, 29
mm diam, bars hardened in oil from 830°C. Izod (2) for steel with 0.25% molybdenum added
Temper brittleness is usually used to describe the notch impact intergranular brittleness (Grain boundaries are
revealed in temper brittle samples by etching in 1 gm cetyl trimethyl ammonium bromide; 20 gm picric acid;
100 cc distilled water, 100 cc ether. Shake mixture, allow to stand for 24 hrs; use portion of top layer and return
to tube afterwards) induced in some steels by slow cooling after tempering above about 600°C and also from
prolonged soaking of tough material between about 400?and 550°C.
Temper brittleness seems to be due to grain boundary enrichment with alloying elements-Mn, Cr, Mo-during
austenitising which leads to enhanced segregation of embattling elements P, Sn, Sb, As-by chemical
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interaction on slow cooling from 600°C. The return to the tough condition, obtained by rehearing embattled
steel to temperatures above 600°C and rapidly cooling, is due to the redistribution and retention in solution of
the embattling segregation. Antimony (0-001 %), phosphorus (0-008 %), arsenic, tin, manganese increase,
while molybdenum decreases the susceptibility of a steel to embattlement. 0-25 % molybdenum reduces the
brittleness as shown by Izod curve No. 2. Table 1 illustrates the effect rate of cooling after tempering and the
influence of an addition of 0-45 % molybdenum:
Table 1. Steel 0.3% C, 3,5 % Ni, 0.7%, Cr, tempered at 630°C
Steel
Cooling
Rate
TS
MPa
Elongation RA
Izod
ft lbf
Izod
J
Ni-Cr Oil 896 18 60 64 87
Ni-Cr Furnance 880 18 60 19 25
Ni-Cr-Mo Furnance 896 18 61 59 80

Nickel And Chromium
Used together for austenitic stainless steels; each element counteracts disadvantages of the other.
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Molybdenum

Molybdenum: A carbide former, prevents brittleness & maintains the steel's strength at high temperatures.
Present in many steels, and air-hardening steels (e.g. A-2, ATS-34) always have 1% or more molybdenum --
molybdenum is what gives those steels the ability to harden in air.

It is Adds greatly to the penetration of hardness and increases toughness of an alloy. It causes steel to resist
softening at high temperatures, which defeats the purpose of forging. If the alloy has below 0.020 percent
molybdenum (Mo), you should be able to forge this alloy with little difficulty.
Molybdenum is used very widely because of its powerful effect in increasing hardenability and also
because in low alloy steels it reduces susceptibility to temper brittleness. It forms stable carbides,
raises the temperature at which softening takes place on tempering and increases resistance to creep.
In high speed steel it can be used to replace approximately twice its weight of tungsten. The corrosion
resistance of stainless steel is improved by molybdenum additions.
Molybdenum increases the hardenability of steel. Molybdenum may produce secondary hardening during the
tempering of quenched steels. It enhances the creep strength of low-alloy steels at elevated temperatures.
Molybdenum substantially increases the resistance to both general and localized corrosion. It increases the
mechanical strength somewhat and strongly promotes a ferritic structure. Molybdenum also promotes the
formation secondary phases in ferritic, ferritic-austenitic and austenitic steels. In martensitic steels it will
increase the hardness at higher tempering temperatures due to its effect on the carbide precipitation.
Molybdenum dissolves in both alpha- and gama-iron and in the presence of carbon forms complex carbides
(FeMo)
6
C, Fe
21
Mo
2
C
6
, Mo
2
C. Molybdenum is similar to chromium in its effect on the shape of the TTT-curve
but up to 0.5% appears to be more effective in retarding pearlite and increasing bainite formation. Additions of
0.5% molybdenum have been made to plain carbon steels to give increased strength at boiler temperatures of
400°C, but the element is mainly used in combination with other alloying elements.

Ni-Cr-Mo steels are widely used for ordnance, turbine rotors and other large articles, since molybdenum tends
to minimize temper brittleness and reduces mass effect. Molybdenum is also a constituent in some high-speed
steels, magnet alloys, heat-resisting and corrosion-resisting steels.
Molybdenum
Strong carbide forming element, and also improves high temperature creep resistance; reduces
temper-brittleness in Ni-Cr steels. Improves corrosion resistance and temper brittleness.



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Vanadium

ƒ Ferrite Promoter.
ƒ Carbide and Nitride Former.

Vanadium acts as a scavenger for oxides, forms vanadium carbide VC, and has a beneficial effect on the
mechanical properties of heat-treated steels, especially in the presence of other elements. It slows up
tempering in the range of 500-600°C and can induce secondary hardening. Chromium-vanadium (0.15%)
steels are used for locomotive forging, automobile axles, coil springs, torsion bars and creep resistance.
Vanadium increases the yield strength and the tensile strength of carbon steel. The addition of small amounts
of Vanadium can significantly increase the strength of steels. Vanadium is one of the primary contributors to
precipitation strengthening in microalloyed steels. When thermomechanical processing TMCP is properly
controlled the ferrite grain size is refined and there is a corresponding increase in toughness. The impact
transition temperature also increases when vanadium is added.
All microalloy steels contain small concentrations of one or more strong carbide and nitride forming
elements. Vanadium, niobium, and titanium combine preferentially with carbon and/or nitrogen to form a fine
dispersion of precipitated particles in the steel matrix.
The presence of vanadium in steel raises the temperature at which grain coarsening sets in and under certain
conditions increases the hardenability. It also lessens softening on tempering and confers secondary hardness
on high speed and other steels. Vanadium carbide is intensely hard and as much as 5% vanadium may be
added to high speed and high chromium tool steel where it improves abrasion resistance. Vanadium is an
important constituent in many types of steel, for widely varying applications, e.g., nitriding, heat-resistance,
tools, wearing plates and other fully hardened parts. In conjunction with molybdenum, vanadium has a marked
effect in enhancing creep resistance.
Vanadium increases the hardness of martensitic steels due to its effect on the type of carbide present. It also
increases tempering resistance. Vanadium stabilises ferrite and will, at high contents, promote ferrite in the
structure. It is only used in hardenable stainless steels.
It retards grain growth within steel even after long exposures at high temperatures, and helps to control grain
structures while heat treating. It is usually present in small quantities of 0.15 to 0.20 percent. Most tool steels
which contain this element seem to absorb shock better that those that do not contain vanadium (V).

Vanadium contributes to wear resistance and hardenability. A carbide former that helps produce fine-grained
steel. A number of steels have vanadium, but M-2, Vascowear, and CPM T440V and 420V (in order of
increasing amounts) have high amounts

Vanadium
Strong carbide forming element; has a scavenging action and produces clean, inclusion free steels. Can cause
re-heat cracking when added to chrome molly steels.
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Tungsten

TUNGSTEN (W): Also known as wolfram, is used as an alloying element in tool steels, as it tends to impart a
tight, small, and dense grain pattern and keen cutting edges when used in relatively small amounts. It will also
cause steel to retain its hardness at higher temperatures and hence will have a detrimental effect upon the
steel's forgeability (otherwise known as "red hard")

Tungsten dissolves in gama-iron and in alpha-iron. With carbon it forms WC and W
2
C, but in the presence of
iron it forms Fe
3
W
3
C or Fe
4
W
2
C. A compound with iron, Fe
3
W
2
provides an age-hardening system. Tungsten
raises the critical points in steel and the carbides dissolve slowly over a range of temperature. When
completely dissolved, the tungsten renders transformation sluggish, especially to tempering, and use is made
of this in most hot-working tool ("high speed") and die steels. It Increases wear resistance. When combined
properly with chromium or molybdenum, tungsten will make the steel to be a high-speed steel. The high-speed
steel M-2 has a high amount of tungsten. Tungsten refines the grain size and produces less tendency to
decarburisation during working. Tungsten is also used in magnet, corrosion- and heat-resisting steels.

The effect of the addition of this metal to steel is to increase the strength at normal and elevated
temperatures. Owing to the hardness of tungsten carbide and its influence on secondary hardening,
tungsten is used as the main alloy addition in high speed tool steels, molybdenum being its only
substitute. In addition, tungsten finds considerable application in general tool steels, die and
precipitation hardening steels. It has found a useful application in valves and other steels required for
use at high temperatures. Tungsten is an essential constituent in the sintered hard metals.
Tungsten
Forms hard and stable carbides; raises the transformation temperature range, and tempering temperatures.
Hardened tungsten steels resist tempering up to 6000C




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Silicon

ƒ Ferrite Former.
ƒ Encourage Brittleness.
Silicon Si, is one of the principal deoxidizers used in steelmaking. Silicon is less effective than manganese in
increasing as-rolled strength and hardness. In low-carbon steels, silicon is generally detrimental to surface
quality. Silicon increases the resistance to oxidation, both at high temperatures and in strongly oxidising
solutions at lower temperatures. It promotes a ferritic structure.
It has a beneficial effect upon tensile strength and improves hardenability of an alloy. It has a toughening
effect when used in combination with certain other elements. Silicon (Si) is usually added to improve
electrical
conductivity of an alloy. Its average concentration is between 1.5 and 2.5 percent.
Silicon is used as a deoxidizer in the manufacture of steel. It slightly increases the strength of ferrite, and when
used in conjunction with other alloys can help increase the toughness and hardness penetration of steel.
Silicon is a powerful deoxidizer, and as such is used in steel making processes in amounts up to about
0·8%. When used as an alloying element, silicon in small percentages will increase the tensile strength
and yield point of structural steels. It is used in amounts of 1·5% to 2% in silicon-manganese spring
steels and ultra-high tensile steels due to its effect in raising the limit of proportionality and resistance
to tempering. Up to 4% in heat resisting steels improves scale resistance owing to the formation of a
protective layer (see also Ihrigizing). The higher the silicon, the higher the temperature at which
protection against further atmospheric oxidation is given. Water vapour and carbon dioxide, however,
attack the layer. Alloys of iron and silicon, containing 15% of the element, are used as acid-resisting
materials, but have the properties of cast irons rather than of steels. Carbon-free alloys with up to 4%
silicon have a high electrical resistance and low hysteresis loss, and are used as transformer steels. In
cast iron, silicon not only serves as a deoxidizer but also has a marked graphitizing effect, thus
improving machinability.
Silicon dissolves in the ferrite, of which it is a fairly effective hardener, and raises the Ac change points
and the Ar points when slowly cooled and also reduces the gama-alpha volume change. Only three types
of silicon steel are in common use-one in conjunction with manganese for springs; the second for
electrical purposes, used in sheet form for the construction of transformer cores, and poles of dynamos
and motors, that demand high magnetic permeability and electrical resistance; and the third is used for
automobile valves.

C Si Mn
1. Silico-manganese 0.5 1,5 0.8
2. Silicon steel 0.07 4,3 0.09
3. Silichrome 0.4 3,5 8

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It contributes oxidation resistance in heat-resisting steels and is a general purpose deoxidizes.
In general Silicon strengthens ferrite and raises the transformation temperature temperatures; has a strong graphitizing
tendency. Always present to some extent, because it is used with manganese as a deoxidizer

Copper

ƒ Austenite Former.
ƒ Impair Forging.
ƒ Use as precipitation hardening alloy e.g17-4PH
Copper dissolves in the ferrite to a limited extent; not more than 3.5% is soluble in steels at normalizing
temperatures, while at room temperature the ferrite is saturated at 0.35%. It lowers the critical points, but
insufficiently to produce martensite by air cooling. The resistance to atmospheric corrosion is improved and
copper steels can be temper hardened.
Copper Cu, in significant amounts is detrimental to hot-working steels. Copper negatively affects forge
welding, but does not seriously affect arc or oxyacetylene welding. Copper can be detrimental to surface
quality. Copper is beneficial to atmospheric corrosion resistance when present in amounts exceeding 0.20%.
Weathering steels are sold having greater than 0.20% Copper.
The addition of about 0.20% copper to low carbon steel may increase its resistance to atmospheric
corrosion by as much as 20% to 30%. In amounts of about 0·50% copper appreciably increases the
tensile and yield strengths. The addition of increasing amounts of copper leads to defects in rolling.
High yield point structural steels containing copper, in association with chromium and appreciable
percentages of silicon and phosphorus have been developed. Copper is also added to some stainless
steels to improve corrosion resistance.
Copper enhances the corrosion resistance in certain acids and promotes an austenitic structure. In
precipitation hardening steels copper is used to form the intermetallic compounds that are used to increase the
strength.

Phosphorous

ƒ Embrittlement Effects
ƒ Increase Machinability.
ƒ Undesirable Element.
Phosphorus P, increases strength and hardness and decreases ductility and notch impact toughness of
steel. The adverse effects on ductility and toughness are greater in quenched and tempered higher-carbon
steels. Phosphorous levels are normally controlled to low levels. Higher phosphorus is specified in
low-carbon free-machining steels to improve machinability.
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Although it has been used to increase the tensile strength of steel and to improve resistance to
atmospheric corrosion, phosphorus is usually regarded as an undesirable impurity because of its
embrittling effect. In most British specifications the maximum permitted is 0.05 %, but in steel for
nitriding it may be restricted to a maximum of 0·02 % since during the nitriding treatment phosphorus
has a temper embrittling effect.

Sulphur

ƒ Increase Machinability.
ƒ Undesirable element.
ƒ Embrittlement Effects.
ƒ Impair Ductility.
ƒ Impair Weldability.

SULFUR S, Is usually regarded as an impurity in most alloys and its addition to steel is held to a minimum as it
is damaging to the hot forming characteristics of steel. It is, however added to increase machinability. A
word of caution, some alloys are offered in different forms, an example is E52100. This particular steel
can be had in either a "Bearing Quality" or "Machining Quality" the latter having sulfur added to increase
machinability.
Sulfur decreases ductility and notch impact toughness especially in the transverse direction. Weldability
decreases with increasing sulfur content. Sulfur is found primarily in the form of sulfide inclusions. Sulfur
levels are normally controlled to low levels. The only exception is free-machining steels, where sulfur is added
to improve machinability.
A non-metal, which combines with iron to form iron sulphides, in which form its effect is to make the
steel red short but combined with manganese its influence is less injurious. In steel the sulphur content
is usually specified as less than 0.05 % but it may be added deliberately to improve machinability.
Sulphur is added to certain stainless steels, the free-machining grades, in order to increase the machinability.
At the levels present in these grades sulphur will substantially reduce corrosion resistance, ductility and
fabrication properties, such as weldability and formability.

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Lead

ƒ Improve Machinability.
ƒ Undesirable Element.
ƒ Impair Ductility.
ƒ Impair Toughness.
ƒ Impair Creep Strength.
Lead Pb, increase the machinability of steel and has no effect upon the other properties of the metal. Lead is
virtually insoluble in liquid or solid steel. However, lead is sometimes added to carbon and alloy steels by
means of mechanical dispersion during pouring to improve the machinability.
The addition of about 025% lead improves machinability. It also causes a reduction in fatigue strength,
ductility and toughness but this only becomes serious in the transverse direction and at high tensile
levels. In creep resisting alloys very small amounts of lead may be harmful.


Hydrogen

Hydrogen H, in steel is an undesirable impurity which is introduced from moisture in the atmosphere or
the charge during melting. If a large amount of hydrogen is present in the liquid steel, some may be
liberated on freezing giving an unsound ingot, evolution of hydrogen subsequently when the solid steel
cools may cause hair line cracks. Hydrogen can be reduced to safe proportions by casting in vacuum
or by prolonged annealing. It may also be introduced into steel by electrolytic action or by pickling and
may then cause brittleness.

Selenium

Selenium Se, A metalloid closely resembling sulphur in its properties. It is sometimes added to steels
to the extent of 0·2 % to 0·3 % to improve machinability.
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Tantalum

Tantalum Ta, This metal is associated with niobium and is very similar to it chemically. As an alloying
addition to steel, niobium is preferred.
Tellurium is added to steel either alone or together with selenium to promote machinability. It is a
powerful carbide stabilizer and has been also added to cast iron where it is said to increase the depth
of chill and to prevent shrinkage. It may be added in small amounts to the molten iron or by the use of
cores dipped or painted with washes containing tellurium in suspension.

Tin

Tin Sn, Owing to its good resistance to corrosion in many conditions, the major use of tin is in the form
of coatings for steel and copper alloys. It is an undesirable impurity in steel giving rise to temper
brittleness, but is less harmful than phosphorus.

Calcium

Calcium Ca, This metal in the form of calcium silicide is sometimes added to steel as a deoxidizer and
degasefier.

Cerium

Cerium Ce, a metal of the rare earth class which in many respects resemble the alkali metals. The hot
working properties of high alloy corrosion- and heat-resistant steels maybe improved by the addition of
cerium, whilst in cast iron, cerium acts as a deoxidizer and desulphurizer but when the sulphur content
has been reduced to a value of about 0·015%, the cerium enters into solution in the cast iron and
functions as a powerful carbide stabilizer. In amounts above 0·02%, cerium is the operative factor in
the production of nodular graphite structures in cast iron.
Cerium is one of the rare earth metals (REM) and is added in small amounts to certain heat resistant
temperature steels and alloys in order to increase the resistance to oxidation and high temperature corrosion.
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Nitrogen

Nitrogen N, Nitrogen can combine with many metals to form nitrides and is thus applied to the case
hardening of steel, the usual source for this purpose being ammonia. The incorporation of nitrogen in
austenitic chromium-nickel steels stabilizes the austenite and increases the strength. In carbon steels it
has an influence on creep. (See Abnormal Steels)
Nitrogen is a very strong austenite former and strongly promotes an austenitic structure. It also substantially
increases the mechanical strength. Nitrogen increases the resistance to localised corrosion, especially in
combination with molybdenum. In ferritic stainless steels nitrogen will strongly reduce toughness and corrosion
resistance. In the martensitic and martensitic-austenitic steels nitrogen increases both hardness and strength
but reduces the toughness.


Boron

Boron B, is added to fully killed steel to improve hardenability. Boron-treated steels are produced to a range of
0.0005 to 0.003%. Whenever boron is substituted in part for other alloys, it should be done only with
hardenability in mind because the lowered alloy content may be harmful for some applications.
The addition of about 0.003 % of boron confers increased harden ability to steels in the quenched and
tempered condition. Further, it has been found that the addition of 0·003% boron to low carbon, 0·50%
molybdenum steel in the normalized condition doubles the yield strength and gives a 30% increase in
tensile strength, but the advantage due to boron is very slight when molybdenum is less than 0.35%
causes difficulty in forging. As much as 2% may be added to steels used in nuclear engineering.
Boron is a potent alloying element in steel. A very small amount of boron (about 0.001%) has a strong effect
on hardenability. Boron steels are generally produced within a range of 0.0005 to 0.003%. Boron is most
effective in lower carbon steels.
Boron. In recent years, especially in USA, 0.003-0.005% boron has been added to previously fully killed,
fine-grain steel to increase the hardenability of the steel. The yield ratio and impact are definitely improved,
provided advantage is taken of the increased hardenability obtained and the steel is fully hardened before
tempering. In conjunction with molybdenum boron forms a useful group of high tensile bainitic steels. Boron is
used in some hard facing alloys and for nuclear control rods.

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Aluminium

Aluminum Al, is widely used as a deoxidizer. Aluminum can control austenite grain growth in reheated steels
and is therefore added to control grain size. Aluminum is the most effective alloy in controlling grain growth
prior to quenching. Titanium, zirconium, and vanadium are also valuable grain growth inhibitors, but there
carbides are difficult to dissolve into solution in austenite.
As a deoxidizer, up to 0.05% aluminum may be added to steel. For increasing fine grain characteristics
or sub-zero impact properties, up to 0·10% may be added. Nitriding steels contain about 1% aluminum
for promoting a high surface hardness when heated in ammonia. Still larger additions made to heat
resisting steels promote resistance to scaling. Approximately 5% added to chromium steel increases
electrical resistivity.
Aluminium improves oxidation resistance, if added in substantial amounts. It is used in certain heat resistant
alloys for this purpose. In precipitation hardening steels aluminium is used to form the intermetallic compounds
that increase the strength in the aged condition.

Zirconium

Zirconium Zr, can be added to killed high-strength low-alloy steels to achieve improvements in inclusion
characteristics. Zirconium causes sulfide inclusions to be globular rather than elongated thus improving
toughness and ductility in transverse bending.
Zirconium acts as a deoxidizing element in steel and combines with the sulphur.

Niobium

Niobium Nb (Columbium) increases the yield strength and, to a lesser degree, the tensile strength of carbon
steel. The addition of small amounts of Niobium can significantly increase the yield strength of
steels. Niobium can also have a moderate precipitation strengthening effect. Its main contributions are to form
precipitates above the transformation temperature, and to retard the recrystallization of austenite, thus
promoting a fine-grain microstructure having improved strength and toughness.
The metal is also known as columbium. It occurs in association with tantalum, to which it is closely
related. Niobium is a strong carbide-forming element and as such is added to certain austenitic
corrosion-resistant steels of the 18/8 chromium-nickel type for the prevention of intercrystalline
corrosion. Where niobium is used as the stabilizer, it is usually specified that it should be present in an
amount at least 8 times that of the carbon content. Further, niobium is often used as a constituent of
the electrodes used in the welding of such steels. Niobium is added to heat-resisting steels and
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enhances creep strength. In small amounts, of the order of 0·05%, it increases the yield strength of
mild steel.
Niobium is both a strong ferrite and carbide former. As titanium it promotes a ferritic structure. In austenitic
steels it is added to improve the resistance to intergranular corrosion but it also enhances mechanical
properties at high temperatures. In martensitic steels niobium lowers the hardness and increases the
tempering resistance. In U.S. it is also referred to as Columbium (Cb).

Titanium

Titanium Ti, is used to retard grain growth and thus improve toughness. Titanium is also used to achieve
improvements in inclusion characteristics. Titanium causes sulfide inclusions to be globular rather than
elongated thus improving toughness and ductility in transverse bending.
Titanium is a strong ferrite former and a strong carbide former, thus lowering the effective carbon content and
promoting a ferritic structure in two ways. In austenitic steels it is added to increase the resistance to
intergranular corrosion but it also increases the mechanical properties at high temperatures. In ferritic stainless
steels titanium is added to improve toughness and corrosion resistance by lowering the amount of interstitials
in solid solution. In martensitic steels titanium lowers the martensite hardness and increases the tempering
resistance. In precipitation hardening steels titanium is used to form the intermetallic compounds that are used
to increase the strength.
The principal use of titanium is to stabilize carbon by forming titanium carbide. In austenitic stainless
steels it is used in this way to prevent inter crystalline corrosion, the titanium addition being at least four
times the carbon content. It is also added to low carbon steels to prevent blistering during vitreous
enameling. Titanium carbide is used with tungsten carbide in the manufacture of hard metal tools.

Cobalt

Cobalt Co, Increases strength and hardness, permits quenching at higher temperatures. In some
steels used for nuclear engineering cobalt is an undesirable impurity, even in amounts as small as
0·02%. Unlike most other alloying elements cobalt reduces hardenability. It raises the red hardness of
steel and this is the reason for adding 5% to 10% cobalt to certain types of high speed steels,
developed for the specific purpose of cutting exceptionally hard materials. Heat resisting alloys with
high cobalt contents have been developed for use in gas turbines. Cobalt is added to the extent of up
to 40 % to magnet steels requiring high coercive force and it is used in electrical- resistance alloys. In
the sintered hard metals Cobalt acts as the binding metal.
Cobalt only used as an alloying element in martensitic steels where it increases the hardness and tempering
resistance, especially at higher temperatures.
Cobalt has a high solubility in alpha- and gama-iron but a weak carbide-forming tendency. It decreases
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Strong carbide forming element. Not used on its own, but added as a carbide stabiliser to some austenitic stainless steels.

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hardenability but sustains hardness during tempering. It is used in "Stellite" type alloys, gas turbine steel,
magnets and as a bond in hard metal.


Tellurium

Tellurium (Te)
Tellurium is added to steel either alone or together with selenium to promote machinability. It is a powerful
carbide stabilizer and has been also added to cast iron where it is said to increase the depth of chill and to
prevent shrinkage. It may be added in small amounts to the molten iron or by the use of cores dipped or
painted with washes containing tellurium in suspension.


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Chapter Three: Articles on alloying elements in steel

Carbon content, steel classifications, and alloy steels

Generally, carbon is the most important commercial steel alloy. Increasing carbon content increases hardness
and strength and improves hardenability. But carbon also increases brittleness and reduces weldability
because of its tendency to form martensite. This means carbon content can be both a blessing and a curse
when it comes to commercial steel.
And while there are steels that have up to 2 percent carbon content, they are the exception. Most steel
contains less than 0.35 percent carbon. To put this in perspective, keep in mind that’s 35/100 of 1 percent.
Now, any steel in the 0.35 to 1.86 percent carbon content range can be hardened using a heat-quench-temper
cycle. Most commercial steels are classified into one of three groups:
1. Plain carbon steels
2. Low-alloy steels
3. High-alloy steels
Plain Carbon Steels
These steels usually are iron with less than 1 percent carbon, plus small amounts of manganese, phosphorus,
sulfur, and silicon. The weldability and other characteristics of these steels are primarily a product of carbon
content, although the alloying and residual elements do have a minor influence.
Plain carbon steels are further subdivided into four groups:
1. Low
2. Medium
3. High
4. Very high
Low. Often called mild steels, low-carbon steels have less than 0.30 percent carbon and are the most
commonly used grades. They machine and weld nicely and are more ductile than higher-carbon steels.
Medium. Medium-carbon steels have from 0.30 to 0.45 percent carbon. Increased carbon means increased
hardness and tensile strength, decreased ductility, and more difficult machining.
High. With 0.45 to 0.75 percent carbon, these steels can be challenging to weld. Preheating, postheating (to
control cooling rate), and sometimes even heating during welding become necessary to produce acceptable
welds and to control the mechanical properties of the steel after welding.
Very High. With up to 1.50 percent carbon content, very high-carbon steels are used for hard steel products
such as metal cutting tools and truck springs. Like high-carbon steels, they require heat treating before, during,
and after welding to maintain their mechanical properties.
Low-alloy Steels
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When these steels are designed for welded applications, their carbon content is usually below 0.25 percent
and often below 0.15 percent. Typical alloys include nickel, chromium, molybdenum, manganese, and silicon,
which add strength at room temperatures and increase low-temperature notch toughness.
These alloys can, in the right combination, improve corrosion resistance and influence the steel’s response to
heat treatment. But the alloys added can also negatively influence crack susceptibility, so it’s a good idea to
use low-hydrogen welding processes with them. Preheating might also prove necessary. This can be
determined by using the carbon equivalent formula, which we’ll cover in a later issue.
High-alloy Steels
For the most part, we’re talking about stainless steel here, the most important commercial high-alloy steel.
Stainless steels are at least 12 percent chromium and many have high nickel contents. The three basic types
of stainless are:
1. Austenitic
2. Ferritic
3. Martensitic
Martensitic stainless steels make up the cutlery grades. They have the least amount of chromium, offer high
hardenability, and require both pre- and postheating when welding to prevent cracking in the heat-affected
zone (HAZ).
Ferritic stainless steels have 12 to 27 percent chromium with small amounts of austenite-forming alloys.
Austenitic stainless steels offer excellent weldability, but austenite isn’t stable at room temperature.
Consequently, specific alloys must be added to stabilize austenite. The most important austenite stabilizer is
nickel, and others include carbon, manganese, and nitrogen. Special properties, including corrosion resistance,
oxidation resistance, and strength at high temperatures, can be incorporated into austenitic stainless steels by
adding certain alloys like chromium, nickel, molybdenum, nitrogen, titanium, and columbium. And while carbon
can add strength at high temperatures, it can also reduce corrosion resistance by forming a compound with
chromium. It’s important to note that austenitic alloys can’t be hardened by heat treatment. That means they
don’t harden in the welding HAZ.
http://www.matter.org.uk/steelmatter/raw_materials/default.htm
Video: Steel Making
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* Stainless steels always have a high chromium content, often considerable amounts of nickel, and sometimes contain
molybdenum and other elements. Stainless steels are identified by a three-digit number beginning with 2, 3, 4, or 5.

Figure 1
Be sure to check the appropriate AISI and SAE publications for the latest revisions.
Steel Classification Systems
Before we look at a couple of common steel classification systems, let’s consider one more high-carbon metal,
cast iron. The carbon content of cast iron is 2.1 percent or more. There are four basic types of cast iron:

1. Gray cast iron, which is relatively soft. It’s easily machined and welded, and you’ll find it used for
engine cylinder blocks, pipe, and machine tool structures.
2. White cast iron, which is hard, brittle, and not weldable. It has a compressive strength of more than
200.000 pounds per square inch (PSI), and when it’s annealed, it becomes malleable cast iron.
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3. Malleable cast iron, which is annealed white cast iron. It can be welded, machined, is ductile, and
offers good strength and shock resistance.
4. Ductile cast iron, which is sometimes called nodular or spheroidal graphite cast iron. It gets this name
because its carbon is in the shape of small spheres, not flakes. This makes it both ductile and
malleable. It’s also weldable.
Now let’s take a look at a typical steel classification system (see Figure 1). Both the Society of Automotive
Engineers (SAE) and the American Iron and Steel Institute (AISI) use virtually identical systems. Both are
based on a four-digit system with the first number usually indicating the basic type of steel and the first two
numbers together indicating the series within the basic alloy group.
Keep in mind there may be a number of series within a basic alloy group, depending on the amount of the
principal alloying elements. The last two or three numbers refer to the approximate permissible range of
carbon content in points (hundredths of a percent).
These classification systems can become fairly complex, and Figure 1 is just a basic representation. Be sure to
reference the most recent AISI and SAE publications for the latest revisions.
That’s a look at some basics concerning the iron-carbon-steel relationship and its influences on welding and
metal alloys. Next time we’ll look at hardening and ways to make metals stronger. We’ll also consider the
influences of some key alloying elements and the effects of welding on metallurgy.


Carbon Steel


Carbon steels and alloy steels are designated by a four digit number, where the first two digits indicate
the alloying elements and the last two digits indicate the amount of carbon, in hundredths of a percent by
weight. For example, a 1060 steel is a plain carbon steel containing 0.60 wt% C.
designation Type
Carbon steels
10xx Plain carbon (Mn 1.00% max)
11xx Resulfurized
12xx Resulfurized and rephosphorized
15xx Plain carbon (Mn 1.00% to 1.65%)
Manganese steels
13xx Mn 1.75%
Nickel steels
23xx Ni 3.50%
25xx Ni 5.00%
Nickel-chromium steels
31xx Ni 1.25%, Cr 0.65% or 0.80%
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32xx Ni 1.25%, Cr 1.07%
33xx Ni 3.50%, Cr 1.50% or 1.57%
34xx Ni 3.00%, Cr 0.77%
Molybdenum steels
40xx Mo 0.20% or 0.25% or 0.25% Mo & 0.042 S
44xx Mo 0.40% or 0.52%
Chromium-molybdenum (Chromoly) steels
41xx Cr 0.50% or 0.80% or 0.95%, Mo 0.12% or 0.20% or 0.25% or 0.30%
Nickel-chromium-molybdenum steels
43xx Ni 1.82%, Cr 0.50% to 0.80%, Mo 0.25%
43BVxx Ni 1.82%, Cr 0.50%, Mo 0.12% or 0.35%, V 0.03% min
47xx Ni 1.05%, Cr 0.45%, Mo 0.20% or 0.35%
81xx Ni 0.30%, Cr 0.40%, Mo 0.12%
81Bxx Ni 0.30%, Cr 0.45%, Mo 0.12%
86xx Ni 0.55%, Cr 0.50%, Mo 0.20%
87xx Ni 0.55%, Cr 0.50%, Mo 0.25%
88xx Ni 0.55%, Cr 0.50%, Mo 0.35%
93xx Ni 3.25%, Cr 1.20%, Mo 0.12%
94xx Ni 0.45%, Cr 0.40%, Mo 0.12%
97xx Ni 0.55%, Cr 0.20%, Mo 0.20%
98xx Ni 1.00%, Cr 0.80%, Mo 0.25%
Nickel-molybdenum steels
46xx Ni 0.85% or 1.82%, Mo 0.20% or 0.25%
48xx Ni 3.50%, Mo 0.25%
Chromium steels
50xx Cr 0.27% or 0.40% or 0.50% or 0.65%
50xxx Cr 0.50%, C 1.00% min
50Bxx Cr 0.28% or 0.50%
51xx Cr 0.80% or 0.87% or 0.92% or 1.00% or 1.05%
51xxx Cr 1.02%, C 1.00% min
51Bxx Cr 0.80%
52xxx Cr 1.45%, C 1.00% min
Chromium-vanadium steels
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61xx Cr 0.60% or 0.80% or 0.95%, V 0.10% or 0.15% min
Tungsten-chromium steels
72xx W 1.75%, Cr 0.75%
Silicon-manganese steels
92xx Si 1.40% or 2.00%, Mn 0.65% or 0.82% or 0.85%, Cr 0.00% or 0.65%
High-strength low-alloy steels
9xx Various SAE grades
xxBxx Boron steels
xxLxx Leaded steels

Stainless steel


ƒ 200 Series: austenitic chromium-nickel-manganese alloys
ƒ 300 Series: austenitic chromium-nickel alloys
ƒ Type 301: highly ductile, for formed products. Also hardens rapidly during mechanical working.
ƒ Type 303: free machining version of 304 via addition of sulfur
ƒ Type 304: the most common; the classic 18/8 stainless steel.
ƒ Type 316: the next most common; for food and surgical stainless steel uses; alloy addition of
molybdenum prevents specific forms of corrosion. 316 steel is more resistant to corrosion than
18-8 stainless steels. 316 steel is used in the handling of certain food and pharmaceutical
products where it is often required in order to minimize metallic contamination. 316 steel is also
known as "marine grade" stainless steel due to its increased ability to resist saltwater corrosion
compared to type 304. SS316 is often used for building nuclear reprocessing plants.
ƒ 400 Series: ferritic and martensitic chromium alloys
ƒ Type 408: heat-resistant; poor corrosion resistance; 11% chromium, 8% nickel.
ƒ Type 409: cheapest type; used for automobile exhausts; ferritic (iron/chromium only).
ƒ Type 410: martensitic (high-strength iron/chromium).
ƒ Type 416: the most machinable stainless steel; achieved by the addition of extra sulfur which
reduces corrosion resistance. Often used for "stainless" rifle barrels
ƒ Type 420: "Cutlery grade" martensitic; similar to the Brearley's original "rustless steel". Also
known as "surgical steel".
ƒ Type 430: decorative, e.g., for automotive trim; ferritic.
ƒ Type 440: a higher grade of cutlery steel, with more carbon in it, which allows for much better
edge retention when the steel is heat treated properly.
ƒ 500 Series: heat resisting chromium alloys
ƒ 600 Series: martensitic precipitation hardening alloys
ƒ Type 630: most common PH stainless, better known as 17-4; 17% chromium, 4% nickel
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Stainless steel designations
SAE
designation
UNS
designation
% Cr % Ni % C % Mn % Si % P % S % N Other
Austenitic
201 S20100 16–18 3.5–5.5 0.15 5.5–7.5 0.75 0.06 0.03 0.25 -
202 S20200 17–19 4–6 0.15 7.5–10.0 0.75 0.06 0.03 0.25 -
205 S20500 16.5–18 1–1.75 0.12–0.25 14–15.5 0.75 0.06 0.03 0.32–0.40 -
301 S30100 16–18 6–8 0.15 2 0.75 0.045 0.03 - -
302 S30200 17–19 8–10 0.15 2 0.75 0.045 0.03 0.1 -
302B S30215 17–19 8–10 0.15 2 2.0–3.0 0.045 0.03 - -
303 S30300 17–19 8–10 0.15 2 1 0.2
0.15
min
-
Mo 0.60
(optional)
303Se S30323 17–19 8–10 0.15 2 1 0.2 0.06 - 0.15 Se min
304 S30400 18–20 8–10.50 0.08 2 0.75 0.045 0.03 0.1 -
304L S30403 18–20 8–12 0.03 2 0.75 0.045 0.03 0.1 -
304Cu S30430 17–19 8–10 0.08 2 0.75 0.045 0.03 - 3–4 Cu
304N S30451 18–20 8–10.50 0.08 2 0.75 0.045 0.03 0.10–0.16 -
305 S30500 17–19 10.50–13 0.12 2 0.75 0.045 0.03 - -
308 S30800 19–21 10–12 0.08 2 1 0.045 0.03 - -
309 S30900 22–24 12–15 0.2 2 1 0.045 0.03 - -
309S S30908 22–24 12–15 0.08 2 1 0.045 0.03 - -
310 S31000 24–26 19–22 0.25 2 1.5 0.045 0.03 - -
310S S31008 24–26 19–22 0.08 2 1.5 0.045 0.03 - -
314 S31400 23–26 19–22 0.25 2 1.5–3.0 0.045 0.03 - -
316 S31600 16–18 10–14 0.08 2 0.75 0.045 0.03 0.10 2.0–3.0 Mo
316L S31603 16–18 10–14 0.03 2 0.75 0.045 0.03 0.10 2.0–3.0 Mo
316F S31620 16–18 10–14 0.08 2 1 0.2
0.10
min
- 1.75–2.50 Mo
316N S31651 16–18 10–14 0.08 2 0.75 0.045 0.03 0.10–0.16 2.0–3.0 Mo
317 S31700 18–20 11–15 0.08 2 0.75 0.045 0.03 0.10 max 3.0–4.0 Mo
317L S31703 18–20 11–15 0.03 2 0.75 0.045 0.03 0.10 max 3.0–4.0 Mo
321 S32100 17–19 9–12 0.08 2 0.75 0.045 0.03 0.10 max
Ti 5(C+N)
min, 0.70 max
329 S32900 23–28 2.5–5 0.08 2 0.75 0.04 0.03 - 1–2 Mo
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330 N08330 17–20 34–37 0.08 2 0.75–1.50 0.04 0.03 - -
347 S34700 17–19 9–13 0.08 2 0.75 0.045 0.030 -
Nb + Ta, 10 x
C min, 1 max
348 S34800 17–19 9–13 0.08 2 0.75 0.045 0.030 -
Nb + Ta, 10 x
C min, 1 max,
but 0.10 Ta
max; 0.20 Ca
384 S38400 15–17 17–19 0.08 2 1 0.045 0.03 - -
Ferritic
405 S40500 11.5–14.5 - 0.08 1 1 0.04 0.03 -
0.1–0.3 Al,
0.60 max
409 S40900 10.5–11.75 0.05 0.08 1 1 0.045 0.03 -
Ti 6 x C, but
0.75 max
429 S42900 14–16 0.75 0.12 1 1 0.04 0.03 - -
430 S43000 16–18 0.75 0.12 1 1 0.04 0.03 - -
430F S43020 16–18 - 0.12 1.25 1 0.06
0.15
min
-
0.60 Mo
(optional)
430FSe S43023 16–18 - 0.12 1.25 1 0.06 0.06 - 0.15 Se min
434 S43400 16–18 - 0.12 1 1 0.04 0.03 - 0.75–1.25 Mo
436 S43600 16–18 - 0.12 1 1 0.04 0.03 -
0.75–1.25
Mo; Nb+Ta 5
x C min, 0.70
max
442 S44200 18–23 - 0.2 1 1 0.04 0.03 - -
446 S44600 23–27 0.25 0.2 1.5 1 0.04 0.03 - -
Martensitic
403 S40300 11.5–13.0 0.60 0.15 1 0.5 0.04 0.03 - -
410 S41000 11.5–13.5 0.75 0.15 1 1 0.04 0.03 - -
414 S41400 11.5–13.5 1.25–2.50 0.15 1 1 0.04 0.03 - -
416 S41600 12–14 - 0.15 1.25 1 0.06
0.15
min
-
0.060 Mo
(optional)
416Se S41623 12–14 - 0.15 1.25 1 0.06 0.06 - 0.15 Se min
420 S42000 12–14 - 0.15 min 1 1 0.04 0.03 - -
420F S42020 12–14 - 0.15 min 1.25 1 0.06
0.15
min
-
0.60 Mo max
(optional)
422 S42200 11.0–12.5 0.50–1.0 0.20–0.25 0.5–1.0 0.5 0.025 0.025 -
0.90–1.25
Mo;
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0.20–0.30 V;
0.90–1.25 W
431 S41623 15–17 1.25–2.50 0.2 1 1 0.04 0.03 - -
440A S44002 16–18 - 0.60–0.75 1 1 0.04 0.03 - 0.75 Mo
440B S44003 16–18 - 0.75–0.95 1 1 0.04 0.03 - 0.75 Mo
440C S44004 16–18 - 0.95–1.20 1 1 0.04 0.03 - 0.75 Mo
Heat resisting
501 S50100 4–6 - 0.10 min 1 1 0.04 0.03 - 0.40–0.65 Mo
502 S50200 4–6 - 0.1 1 1 0.04 0.03 - 0.40–0.65 Mo


Unified numbering system
Introduction to the Unified Numbering System of Ferrous Metals and Alloys
http://www.key-to-steel.com/Articles/Art111.htm
http://en.wikipedia.org/wiki/Unified_numbering_system



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Strength in Steel


Strength in steels arises from several phenomena, which usually contribute collectively to the observed
mechanical properties. The heat treatment of steels is aimed at adjusting these contributions so that the
required balance of mechanical properties is achieved. Fortunately the γ/α phase change allows great
variations in microstructure to be produced, so that a wide range of mechanical properties can be obtained
even in plain carbon steels. The additional use of metallic alloying elements, primarily as a result of their
influence on the transformation, provides an even greater control over microstructure, with consequent
benefits in the mechanical properties


The simplest version of analyzes the effects of alloying elements on iron-carbon alloys would require analysis of
a large number of ternary alloy diagrams over a wide temperature range. However, Wever pointed out that iron
binary equilibrium systems fall into four main categories (Fig. 1): open and closed γ-field systems, and expanded
and contracted γ-field systems. This approach indicates that alloying elements can influence the equilibrium
diagram in two ways:
by expanding the γ-field, and encouraging the formation of austenite over wider compositional limits. These
elements are called γ-stabilizers.
by contracting the γ-field, and encouraging the formation of ferrite over wider compositional limits. These
elements are called α-stabilizers.
The form of the diagram depends to some degree on the electronic structure of the alloying elements which is
reflected in their relative positions in the periodic classification.

Class 1: open γ-field. To this group belong the important steel alloying elements nickel and manganese, as well
as cobalt and the inert metals ruthenium, rhodium, palladium, osmium, iridium and platinum. Both nickel and
manganese, if added in sufficiently high concentration, completely eliminate the bcc α-iron phase and replace it,
down to room temperature, with the γ-phase. So nickel and manganese depress the phase transformation from γ
to α to lower temperatures (Fig. 1a), i.e. both Ac1 and Ac3 are lowered. It is also easier to obtain metastable
austenite by quenching from the γ-region to room temperature, consequently nickel and manganese are useful
elements in the formulation of austenitic steels.
Class 2: expanded γ-field. Carbon and nitrogen are the most important elements in this group. The γ-phase field
is expanded, but its range of existence is cut short by compound formation (Fig.1b). Copper, zinc and gold have
a similar influence. The expansion of the γ-field by carbon, and nitrogen, underlies the whole of the heat
treatment of steels, by allowing formation of a homogeneous solid solution (austenite) containing up to 2.0 wt %
of carbon or 2.8 wt % of nitrogen.
Class 3: closed γ-field. Many elements restrict the formation of γ-iron, causing the γ-area of the diagram to
contract to a small area referred to as the gamma loop (Fig. 1c). This means that the relevant elements are
encouraging the formation of bcc iron (ferrite), and one result is that the δ- and γ-phase fields become
continuous. Alloys in which this has taken place are, therefore, not amenable to the normal heat treatments
involving cooling through the γ/α-phase transformation. Silicon, aluminium, beryllium and phosphorus fall into
this category, together with the strong carbide forming elements, titanium, vanadium, molybdenum and
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chromium.



Figure 1. Classification of iron alloy phase diagrams: a. open γ-field; b. expanded γ-field; c. closed γ-field

Class 4: contracted y-field. Boron is the most significant element of this group, together with the carbide forming
elements tantalum, niobium and zirconium. The γ-loop is strongly contracted, but is accompanied by compound
formation (Fig. 1d).
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The distribution of alloying elements in steels. Although only binary systems have been considered so far, when
carbon is included to make ternary systems the same general principles usually apply. For a fixed carbon content,
as the alloying clement is added the y-field is either expanded or contracted depending on the particular solute.
With an element such as silicon the γ-field is restricted and there is a corresponding enlargement of the α-field. If
vanadium is added, the γ-field is contracted and there will be vanadium carbide in equilibrium with ferrite over
much of the ferrite field. Nickel does not form a carbide and expands the γ-field. Normally elements with
opposing tendencies will cancel each other out at the appropriate combinations, but in some cases anomalies
occur. For example, chromium added to nickel in a steel in concentrations around 18% helps to stabilize the
γ-phase, as shown by 18Cr8Ni austenitic steels.
One convenient way of illustrating quantitatively the effect of an alloying element on the γ-phase field of the Fe-C
system is to project on to the Fe-C plane of the ternary system the γ-phase field boundaries for increasing
concentration of a particular alloying element. For more precise and extensive information, it is necessary to
consider series of isothermal sections in true ternary systems Fe-C-X, but even in some of the more familiar
systems the full information is not available, partly because the acquisition of accurate data can be a difficult and
very time-consuming process.
Recently the introduction of computer-based methods has permitted the synthesis of extensive thermochemical
and phase equilibria data, and its presentation in the form, for example, of isothermal sections over a wide range
of temperatures.
If only steels in which the austenite transforms to ferrite and carbide on slow cooling are considered, the alloying
elements can be divided into three categories:
elements which enter only the ferrite phase
elements which form stable carbides and also enter the ferrite phase
elements which enter only the carbide phase.
In the first category there are elements such as nickel, copper, phosphorus and silicon which, in transformable
steels, are normally found in solid solution in the ferrite phase, their solubility in cementite or in alloy carbides
being quite low.
The majority of alloying elements used in steels fall into the second category, in so far as they are carbide
formers and as such, at low concentrations, go into solid solution in cementite, but will also form solid solutions in
ferrite. At higher concentrations most will form alloy carbides, which are thermodynamically more stable than
cementite.
Typical examples are manganese, chromium, molybdenum, vanadium, titanium, tungsten and niobium.
Manganese carbide is not found in steels, but instead manganese enters readily into solid solution in Fe3C. The
carbide-forming elements are usually present greatly in excess of the amounts needed in the carbide phase,
which are determined primarily by the carbon content of the steel. The remainder enters into solid solution in the
ferrite with the non-carbide forming elements nickel and silicon. Some of these elements, notably titanium,
tungsten, and molybdenum, produce substantial solid solution hardening of ferrite.
In the third category there are a few elements which enter predominantly the carbide phase. Nitrogen is the most
important element and it forms carbo-nitrides with iron and many alloying elements. However, in the presence of
certain very strong nitride forming elements, e.g. titanium and aluminum, separate alloy nitride phases can occur.
While ternary phase diagrams, Fe-C-X, can be particularly helpful in understanding the phases which can exist in
simple steels, isothermal sections for a number of temperatures are needed before an adequate picture of the
equilibrium phases can be built up. For more complex steels the task is formidable and equilibrium diagrams can
only give a rough guide to the structures likely to be encountered. It is, however, possible to construct
pseudobinary diagrams for groups of steels, which give an overall view of the equilibrium phases likely to be
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encountered at a particular temperature.
Structural changes resulting from alloying additions. The addition to iron-carbon alloys of elements such as nickel,
silicon, manganese, which do not form carbides in competition with cementite, does not basically alter the
microstructures formed after transformation. However, in the case of strong carbide-forming elements such as
molybdenum, chromium and tungsten, cementite will be replaced by the appropriate alloy carbides, often at
relatively low alloying element concentrations. Still stronger carbide forming elements such as niobium, titanium
and vanadium are capable of forming alloy carbides, preferentially at alloying concentrations less than 0.1 wt%.
It would, therefore, be expected that the microstructures of steels containing these elements would be radically
altered. It has been shown how the difference in solubility of carbon in austenite and ferrite leads to the familiar
ferrite/cementite aggregates in plain carbon steels. This means that, because the solubility of cementite in
austenite is much greater than in ferrite, it is possible to redistribute the cementite by holding the steel in the
austenite region to take it into solution, and then allowing transformation to take place to ferrite and cementite.
Examining the possible alloy carbides, and nitrides, in the same way, shows that all the familiar ones are much
less soluble in austenite than is cementite.
Chromium and molybdenum carbides are not included, but they are substantially more soluble in austenite than
the other carbides. Detailed consideration of such data, together with practical knowledge of alloy steel behavior,
indicates that, for niobium and titanium, concentrations of greater than about 0.25 wt % will form excess alloy
carbides which cannot be dissolved in austenite at the highest solution temperatures. With vanadium the limit is
higher at 1-2%, and with molybdenum up to about 5%. Chromium has a much higher limit before complete
solution of chromium carbide in austenite becomes difficult. This argument assumes that sufficient carbon is
present in the steel to combine with the alloying element. If not, the excess metallic element will go into solid
solution both in the austenite and the ferrite.
In general, the fibrous morphology represents a closer approach to an equilibrium structure so it is more
predominant in steels which have transformed slowly. In contrast, the interphase precipitation and dislocation
nucleated structures occur more readily in rapidly transforming steels, where there is a high driving force, for
example, in microalloyed steels.
The clearest analogy with pearlite is found when the alloy carbide in lath morphology forms nodules in
association with ferrite. These pearlitic nodules are often encountered at temperatures just below Ac1, in steels
which transform relatively slowly.
For example, these structures are obtained in chromium steels with between 4% and 12% chromium and the
crystallography is analogous to that of cementitic pearlite. It is, however, different in detail because of the
different crystal structures of the possible carbides. The structures observed are relatively coarse, but finer than
pearlite formed under equivalent conditions, because of the need for the partition of the alloying element, e.g.
chromium between the carbide and the ferrite. To achieve this, the interlamellar spacing must be substantially
finer than in the equivalent iron-carbon case.
Interphase precipitation. Interphase precipitation has been shown to nucleate periodically at the γ/α interface
during the transformation. The precipitate particles form in bands which are closely parallel to the interface, and
which follow the general direction of the interface even when it changes direction sharply. A further characteristic
is the frequent development of only one of the possible Widmanstätten variants, for example VC plates in a
particular region are all only of one variant of the habit, i.e. that in which the plates are most nearly parallel to the
interface.
The extremely fine scale of this phenomenon in vanadium steels, which also occurs in Ti and Nb steels, is due to
the rapid rate at which the γ/α transformation takes place. At the higher transformation temperatures, the slower
rate of reaction leads to coarser structures. Similarly, if the reaction is slowed down by addition of further alloying
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elements, e.g. Ni and Mn, the precipitate dispersion coarsens.
The scale of the dispersion also varies from steel to steel, being coarsest in chromium, tungsten and
molybdenum steels where the reaction is relatively slow, and much finer in steels in which vanadium, niobium
and titanium are the dominant alloying elements and the transformation is rapid.
Transformation diagrams for alloy steels. The transformation of austenite below the eutectoid temperature can
best be presented in an isothermal transformation diagram, in which the beginning and end of transformation is
plotted as a function of temperature and time. Such curves are known as time-temperature-transformation, or
TTT curves, and form one of the important sources of quantitative information for the heat treatment of steels.
In the simple case of a eutectoid plain carbon steel, the curve is roughly C-shaped with the pearlite reaction
occurring down to the nose of the curve and a little beyond. At lower temperatures bainite and martensite are
formed. The diagrams become more complex for hypo- and hyper-eutectoid alloys as the ferrite or cementite
reactions have also to be represented by additional lines
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Alloying and Its Effects on the Critical Temperature, Hardness
and Tensile Strength

Alloying elements have significant effect on the iron-iron carbide equilibrium diagram. The addition of some of
these alloying elements will widen the temperature range through which austenite (gamma -iron) is stable while
other elements will constrict the temperature range. What this means is that some elements will raise and some
elements will lower the critical temperature of steel.
Manganese, cobalt, and nickel increase the temperature range through which austenite is stable. This also
means that the lower critical temperature of steel will be lowered by these alloying elements. Other alloying
elements that lower the critical temperature of steel are carbon, copper and zinc. The alloying elements that are
used to reduce the critical temperature are highly soluble in the gamma iron (austenite). Figure 1 shows the
effect of manganese on the critical temperature of steel.

Figure 1. The effect of alloying with manganese on the critical temperature of steel and austenite (γ-iron) phase
transformation zone on the iron-iron carbide diagram..
Alloys such as aluminum, chromium, molybdenum, phosphorus, silicon, tungsten tend to form solid solutions
with alpha iron (ferrite). This constricts the temperature region through which gamma iron (austenite) is stable.
As shown in Figure 2, chromium at different percentages constricts the critical temperature range which results
in a marked reduction of the region where austenite is stable.
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Figure 2. Effect of alloying with chromium on the critical temperature of steel and austenite (g -iron) phase
transformation zone on the iron-iron carbide diagram.
The elements shown in Figure 3 have the greatest solubility in ferrite and also influence the hardenability of iron
when in the presence of carbon. With a slight increase in the carbon content, they respond markedly to heat
treating, because carbon acts as a ferrite strengthener. As indicated in Figure 3, Phosphorus will improve the
hardness of the ferrite significantly by adding only a very small percentage of Phosphorus, while Chromium will
not strengthen the ferrite that well even at very high percentage of Chromium addition to the steel

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Figure 3. The effect of various alloying elements on the hardness of steel.
Figure 4 shows the effect of furnace cooling vs. air cooling on the tensile strength of steel for three different
percentages of carbon in the presence of chromium. As this figure indicates, furnace cooling has very little effect
on the tensile strength of the material. The addition of chromium does not change the tensile strength properties
when the steel is cooled in the furnace. If the same steels are air cooled at the same rate, the slope of the curves
increases significantly which means that a slight increase in the chromium content increases the strength
drastically when air cooling is applied.

Figure 4. Effect of different percentages of carbon on the tensile strength of steel in the presence of chromium.

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Control of High Strength Low Alloy (HSLA) Steel Properties


Most HSLA steels are furnished in the as-hot-rolled condition with ferritic-pearlitic microstructure. The exceptions
are the controlled-rolled steels with an acicular ferrite microstructure and the dual-phase steels with martensite
dispersed in a matrix of polygonal ferrite. These two types of HSLA steels use the formation of eutectoid
structures for strengthening, while the ferritic-pearlitic HSLA steels generally require strengthening of the ferrite.
Pearlite is generally an undesirable strengthening agent in structural steels because it reduces impact toughness
and requires higher carbon contents. Moreover, yield strength is largely unaffected by a higher pearlite content.
Strengthening Mechanisms in Ferrite
The ferrite in HSLA steels is typically strengthened by grain refinement, precipitation hardening, and, to a lesser
extent, solid-solution strengthening. Grain refinement is the most desirable strengthening mechanism because it
improves not only strength but also toughness.
Grain refinement is influenced by the complex effects of alloy design and processing methods. For example, the
various methods of grain refinement used in the three different stages of hot rolling (that is, reheating, hot rolling,
and cooling) include:
The addition of titanium or aluminum to retard austenite grain growth when the steel is reheated for hot
deformation or subsequent heat treatment
The controlled rolling of microalloyed steels to condition the austenite so that it transforms into fine-grain ferrite
The use of alloy additions and/or faster cooling rates to lower the austenite-to-ferrite transformation temperature.
The use of higher cooling rates for grain refinement may require consideration of its effect on precipitation
strengthening and the possibility of undesirable transformation products.
Precipitation strengthening occurs from the formation of finely dispersed carbonitrides developed during heating
and cooling. Because precipitation strengthening is generally associated with a reduction in toughness, grain
refinement is often used in conjunction with precipitation strengthening to improve toughness.
Precipitation strengthening is influenced by the type of carbonitride, its grain size, and, of course, the number of
carbonitrides precipitated. The formation of MC is the most effective metal carbide in the precipitation
strengthening of microalloyed niobium, vanadium, and/or titanium steels. The number of fine MC particles
formed during heating and cooling depends on the solubility of the carbides in austenite and on cooling rates.
Steelmaking
Precise steelmaking operations are also essential in controlling the properties and chemistry of HSLA steels.
Optimum property levels depend on such factors as the control of significant alloying elements and the reduction
of impurities and nonmetallic inclusions.
Developments in secondary steelmaking such as desulphurization, vacuum degassing, and argon shrouding
have enabled better control of steel chemistry and the effective use of microalloyed elements. Compositional
limits for HSLA steel grades described in ASTM specifications the use of vacuum degassing equipment allows
the production of interstitial-free (IF) steels. The IF steels exhibit excellent formability, high elongation, and good
deep draw/ability.
Compositions and Alloying Elements
Chemical compositions for the HSLA steels are specified by ASTM standards. The principal function of alloying
elements in these ferrite-pearlite HSLA steels, other than corrosion resistance, is strengthening of the ferrite by
grain refinement, precipitation strengthening, and solid-solution strengthening. Solid-solution strengthening is
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closely related to alloy contents, while grain refinement and precipitation strengthening depend on the complex
effects of alloy design and thermo-mechanical treatment.
Alloying elements are also selected to influence transformation temperatures so that the transformation of
austenite to ferrite and pearlite occurs at a lower temperature during air cooling. This lowering of the
transformation temperature produces a finer-grain transformation product, which is a major source of
strengthening. At the low carbon levels typical of HSLA steels, elements such as silicon, copper, nickel, and
phosphorus are particularly effective for producing fine pearlite. Element such as, manganese and chromium,
which are present in both the cementite and ferrite, also strengthen the ferrite by solid-solution strengthening in
proportion to the amount, dissolved in the ferrite.
In the presence of alloying elements, the practical maximum carbon content at which HSLA steels can be used in
the as-cooled condition is approximately 0.20%. Higher levels of carbon tend to form martensite or bainite in the
microstructure of as-rolled steels, although some of the higher-strength low-alloy steels have carbon contents
that approach 0.30%.
The required strength is developed by the combined effect of:
Fine grain size developed during controlled hot roiling and enhanced by microalloyed elements (especially
niobium)
Precipitation strengthening caused by the presence of vanadium, niobium, and titanium in the composition.
Nitrogen additions to high-strength steels containing vanadium are limited to 0.005% and have become
commercially important because such additions enhance precipitation hardening. The precipitation of vanadium
nitride in vanadium-nitrogen steels also improves grain refinement because it has a lower solubility in austenite
than vanadium carbide.
Manganese is the principal strengthening element in plain carbon high-strength structural steels. It functions
mainly as a mild solid-solution strengthener in ferrite, but it also provides a marked decrease in the
austenite-to-ferrite transformation temperature. In addition, manganese can enhance the precipitation
strengthening of vanadium steels and. to a lesser extent, niobium steels.
One of the most important applications of silicon is its use as a deoxidizer in molten steel. Silicon has a
strengthening effect in low-alloy structural steels. In larger amounts, it increases resistance to scaling at elevated
temperatures. Silicon has a significant effect on yield strength enhancement by solid-solution strengthening and
is widely used in HSLA steels for riveted or bolted structures.
Copper in levels in excess of 0.50% also increases the strength of both low- and medium-carbon steels by virtue
of ferrite strengthening, which is accompanied by only slight decreases in ductility. Copper can be retained in
solid solution even at the slow rate of cooling obtained when large sections are normalized, but it is precipitated
out when the steel is reheated to about 510 to 605°C (950 to 1125°F). At about 1% copper, the yield strength is
increased by about 70 to 140 MPa regardless of the effects of other alloying elements. Copper in amounts up to
0.75% is considered to have only minor adverse effects on notch toughness or weldability. Copper precipitation
hardening gives the steel the ability to be formed extensively and then precipitation hardened as a complex
shape or welded assembly.
The atmospheric-corrosion resistance of steel is increased appreciably by the addition of phosphorus, and when
small amounts of copper are present in the steel, the effect of the phosphorus is greatly enhanced. When both
phosphorus and copper are present, there is a greater beneficial effect on corrosion resistance than the sum of
the effects of the individual elements.
Chromium is often, added with copper to obtain improved atmospheric-corrosion resistance.
Nickel is often added to copper-bearing steels to minimize hot shortness.
Molybdenum in hot-rolled HSLA steels is used primarily to improve hardenability when transformation products
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other than ferrite-pearlite are desired. Molybdenum (0.15 to 0.30%) in microalloyed steels also increases the
solubility of niobium in austenite, thereby enhancing the precipitation of NbC(N) in the ferrite. This increases the
precipitation-strengthening effect of NbC(N).
Aluminum is widely used as a deoxidizer and was the first element used to control austenite grain growth during
reheating. During controlled rolling, niobium and titanium are more effective grain refiners than aluminum.
Vanadium strengthens HSLA steels by both precipitation hardening the ferrite and refining the ferrite grain size.
The precipitation of vanadium carbonitride in ferrite can develop a significant increase in strength that depends
not only on the rolling process used, but also on the base composition. Carbon contents above 0.13 to 0.15%
and manganese content of 1% or more enhances the precipitation hardening, particularly when the nitrogen
content is at least 0.01%.
Titanium is unique among common alloying elements in that it provides both precipitation strengthening and
sulfide shape control. Small amounts of titanium (<0.025%) are also useful in limiting austenite grain growth.
However, it is useful only in fully killed (aluminum deoxidized) steels because of its strong deoxidizing effects, the
versatility of titanium is limited because variations in oxygen, nitrogen, and sulfur affect the contribution of
titanium as carbide strengthened.
Zirconium can also be added to killed high-strength low-alloy steels to improve inclusion characteristics,
particularly in the case of sulfide inclusions, for which changes in inclusion shape improve ductility in transverse
bending.
Boron has no effect on the strength of normal hot-rolled steel but can considerably improve hardenability when
transformation products such as acicular ferrite are desired in low-carbon hot-rolled plate.
Treatment with calcium is preferred for sulfide inclusion shape control.
Controlled Rolling
The hot-rolling process has gradually become a much more closely controlled operation, and controlled rolling is
now being increasingly applied to microalloyed steels with compositions carefully chosen to provide optimum
mechanical properties at room temperature.
Controlled rolling is a procedure whereby the various stages of rolling are temperature controlled, with the
amount of reduction in each pass predetermined and the finishing temperature precisely defined. This
processing is widely used to obtain reliable mechanical properties in steels for pipelines, bridges, offshore
platforms, and many other engineering applications. The use of controlled rolling has resulted in improved
combinations of strength and toughness and further reductions in the carbon content of microalloyed HSLA
steels

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Influence of Alloying Elements on Steel Microstructure

It is a long-standing tradition to discuss the various alloying elements in terms of the properties they confer on
steel. For example, the rule was that Chromium (Cr) makes steel hard whereas Nickel (Ni) and Manganese (Mn)
make it tough. In saying this, one had certain types of steel in mind and transferred the properties of particular
steel to the alloying element that was thought to have the greatest influence on the steel under consideration.
This method of reasoning can give false impressions and the following examples will illustrate this point.

When we say that Cr makes steel hard and wear-resisting we probably associate this with the 2% C, 12% Cr tool
steel grade, which on hardening does in fact become very hard and hard-wearing. But if, on the other hand, we
choose a steel containing 0.10% C and 12% Cr, the hardness obtained on hardening is very modest.
It is quite true that Mn increases steel toughness if we have in mind the 13% manganese steel, so-called
Hadfield steel. In concentrations between l% and 5%, however, Mn can produce a variable effect on the
properties of the steel it is alloyed with. The toughness may either increase or decrease.
A property of great importance is the ability of alloying elements to promote the formation of a certain phase or to
stabilize it. These elements are grouped as austenite-forming, ferrite-forming, carbide-forming and
nitride-forming elements.

Austenite-forming elements
The elements C, Ni and Mn are the most important ones in this group. Sufficiently large amounts of Ni or Mn
render a steel austenitic even at room temperature. An example of this is the so-called Hadfield steel which
contains 13% Mn, 1,2% Cr and l% C. In this steel both the Mn and C take part in stabilizing the austenite.
Another example is austenitic stainless steel containing 18% Cr and 8% Ni.
The equilibrium diagram for iron-nickel, Figure 1, shows how the range of stability of austenite increases with
increasing Ni-content.
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Figure 1. Fe-Ni equilibrium diagram
More diagrams: http://www.calphad.com/phase_diagrams.html

An alloy containing 10% Ni becomes wholly austenitic if heated to 700°C. On cooling, transformation from g to a
takes place in the temperature range 700-300°C.
Ferrite-forming elements
The most important elements in this group are Cr, Si, Mo, W and Al. The range of stability of ferrite in
iron-chromium alloys is shown in Figure 2. Fe-Cr alloys in the solid state containing more than 13% Cr are ferritic
at all temperatures up to incipient melting. Another instance of ferritic steel is one that is used as transformer
sheet material. This is a low-carbon steel containing about 3% Si.










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Figure 2. Cr-Fe equilibrium diagram

Multi-alloyed steels
The great majority of steels contain at least three components. The constitution of such steels can be deduced
from ternary phase diagrams (3 components). The interpretation of these diagrams is relatively difficult and they
are of limited value to people dealing with practical heat treatment since they represent equilibrium conditions
only. Furthermore, since most alloys contain more than three components it is necessary to look for other ways
of assessing the effect produced by the alloying elements on the structural transformations occurring during heat
treatment.
One approach that is quite good is the use of Schaeffler diagrams (see Figure 3). Here the austenite formers are
set out along the ordinate and the ferrite formers along the abscissa. The original diagram contained only Ni and
Cr but the modified diagram includes other elements and gives them coefficients that reduce them to the
equivalents of Ni or Cr respectively. The diagram holds good for the rates of cooling which result from welding.
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Figure 3. Modified Schaeffler diagram
A 12% Cr steel containing 0.3% C is martensitic, the 0.3% C gives the steel a nickel equivalent of 9. An 18/8 steel
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(18% Cr, 8% Ni) is austenitic if it contains 0-0.5% C and 2% Mn. The Ni content of such steels is usually kept
between 9% and 10%.
Hadfield steel with 13% Mn (mentioned above) is austenitic due to its high carbon content. Should this be
reduced to about 0.20% the steel becomes martensitic.
Carbide-forming elements
Several ferrite formers also function as carbide formers. The majority of carbide formers are also ferrite formers
with respect to Fe. The affinity of the elements in the line below for carbon increases from left to right.
Cr, W, Mo, V, Ti, Nb, Ta, Zr.
Some carbides may be referred to as special carbides, i.e. non-iron-containing carbides, such as Cr7C3 W2C,
VC, Mo2C. Double or complex carbides contain both Fe and a carbide-forming element, for example Fe4W2C.
High-speed and hot-work tool steels normally contain three types of carbides, which are usually designated M6C,
M23C6 and MC. The letter M represents collectively all the metal atoms. Thus M6C represents Fe4W2C or
Fe4Mo2C; M23C6 represents Cr23C6 and MC represents VC or V4C3.
Carbide stabilizers
The stability of the carbides is dependent on the presence of other elements in the steel. How stable the carbides
are depends on how the element is partitioned between the cementite and the matrix. The ratio of the
percentage, by weight, of the element contained in each of the two phases is called the partition coefficient K.
The following values are given for K:

Al Cu P Si Co Ni W Mo Mn Cr Ti Nb Ta
0 0 0 0 0.2 0.3 2 8 11,4 28 Increasing

Note that Mn, which by itself is a very weak carbide former, is a relatively potent carbide stabilizer. In practice, Cr
is the alloying element most commonly used as a carbide stabilizer.
Malleable cast iron (i.e. white cast iron that is rendered soft by a graphitizing heat treatment called malleablizing)
must not contain any Cr. Steel containing only Si or Ni is susceptible to graphitization, but this is most simply
prevented by alloying with Cr.
Nitride-forming elements
All carbide formers are also nitride formers. Nitrogen may be introduced into the surface of the steel by nitriding.
By measuring the hardness of various nitrided alloy steels it is possible to investigate the tendency of the
different alloying elements to form hard nitrides or to increase the hardness of the steel by a mechanism known
as precipitation hardening.
The results obtained by such investigations are shown in Figure 4, from which it can be seen that very high
hardnesses result from alloying a steel with Al or Ti in amounts of about 1,5%.
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Figure 4. Effect of alloying element additions on hardness after nitriding Base composition: 0.25% C, 0.30% Si,
0.70% Mn

On nitriding the base material in Figure 4, hardness of about 400 HV is obtained and according to the diagram
the hardness is unchanged if the steel is alloyed with Ni since this element is not a nitride former and hence does
not contribute to any hardness increase
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Martensite in Austenitic Stainless Steel Welds

Background
Martensite is a crystal structure that forms in steels during rapid cooling. Cooling rates are dependent on the
particular chemistry of the steel. Certain conditions can be met that will cause martensite formation in austenitic
stainless steels.
Long, needle-like clusters of crystals in the metal characterize martensite. The martensite crystals have a highly
stressed body centered tetragonal structure. In austenitic stainless steels and the austenite phase of a magnetic
(austenitic/ferritic) stainless, when martensite is present in a weld, don't expect it to pass the bend test. The weld
will not have the toughness and ductility that we normally expect from a stainless steel, and in some
circumstances there may be unanticipated corrosion.
Fillet Composition
With only one exception, adding alloying elements to steel allows martensite to form at a slower cooling rate.
That exception is cobalt, which works the other way. With cobalt, martensite will form at a faster cooling rate.
We recognize that the actual composition of the weld fillet will vary along a line running across or bisecting the
weld fillet. On the centerline, we expect the fillet composition to be closer to the wire composition. Approaching
each base metal, the composition shifts from the filler metal composition towards each base metal. In welding
metallurgy, we mark on the phase diagram the chemistry of one base metal and the chemistry of the filler wire.
We find that the actual fillet compositions lie on the line drawn on the phase diagram. When the base metals are
different, it takes different lines on the phase diagram to represent the compositions approaching each base
metal.
Predicting Martensite
The results and microstructural consequences of this sort of exercise in physical metallurgy appeared in 1949 as
the "Schaeffler Diagram". Our technology did not stand still and the Diagram iterated through several updates.
The 1994 Winter Addendum to the ASME Code brought us the Welding Research Council's "WRC-1992
Diagram" which continues to be extensively used. Still, there has been a problem associated with manganese,
which brought yet another modification into use. The analysis behind the modification appears, for example, in
D.J. Kotecki's, "A martensite boundary on the WRC-1992 diagram" (Welding Journal , Vol. 78, No. 5, pp
180-192).
In lots of cases the 1% manganese line satisfactorily predicts martensite or not martensite. However, we
sometimes encounter steels having higher manganese and quite often encounter much lower. High side
examples include 1.0-1.5% manganese in a 309L filler wire, 4% in a 307, and 6% in the European 18 8 Mn filler
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wire. On the low side, if you are joining stainless to a modern carbon steel, the manganese can be quite low,
perhaps even 0.3%.

(The 1949 Schaeffler diagram - click image to enlarge)
To enter the modified Diagram, we need to calculate two numbers roughly based on chromium and nickel
content. We also have to apply a lot of welding "know-how" as to the mixing of the metals.
Calculate the
Nickel Ni Equivalent = %Ni + 35%C + 20%Mn + 0.25%Cu
Chrome Cr Equivalent = %Cr + Mo + 1.5%Si + 0.7%Nb

The Amount of Nitrogen
One of the problems we have to also confront is the amount of nitrogen. The best shielding practice with a wire
electrode might not introduce nitrogen. Flux cored electrodes tend to add nitrogen. For example, the metal in a
flux cored electrode might analyze to 0.05% nitrogen while it deposits as 0.075% nitrogen. Most of us deal with
the nitrogen by first plotting the points with only the known nitrogen and then we plot the nearby point based on
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our estimate of the actual nitrogen. The compositions at risk are those on the Diagram and below the indicated
manganese brands. Within the bands the diagram is known to be imprecise.
In practice, you have to cope with the range of compositions between one base metal and the filler metal, and
between the other base metal and the filler metal. You could put all of your predicted nickel and chromium
equivalent compositions on the graph. However, examining the diagram we see that the compositions more at
risk for forming martensite are those with low nickel and chromium equivalent numbers, coupled with low
manganese. After a little practice with the diagram we know pretty well which compositions are likely to be at risk
and we tend to plot only those numbers.
A warning: Notice that all of the alloying elements in the calculation contribute to hardenability. Should either
base metal or the filler metal contain any unlisted elements which are known to contribute to hardenability then
the Diagram doesn't apply. After decades of absence, tungsten is showing up mostly as a substitute for
molybdenum and mostly in Russian and Chinese metals. In doing the calculation the practice is to lump the
tungsten with the moly on a 1:1 basis. When forced to do it, welding metallurgists may tweak the calculations a
little to reflect other unlisted elements, however, there isn't much of a research foundation on which to base such
adjustments.
Ferrite Number
The 300 series of stainless steels is austenitic (non-magnetic) while the duplex stainless steels are mixed
austenite and ferrite. In the field, the amount of ferrite is measured through its magnetic response. The portable
meter is calibrated for % ferrite and it is called the "ferrite number". Martensite gives a magnetic response, but
not as strongly as ferrite, so when it is present it contributes to the "ferrite number".
Recognize also that perfectly good austenitic stainless steel that has been heavily cold worked can become
slightly magnetic and give a ferrite number even though ferrite nor martensite are present.
In the upper right side of the diagram there is a cluster of lines of constant ferrite number. The upper left line is
1% ferrite number which is nominally 99% austenite and 1% ferrite. The last line along the lower right side of the
cluster is nominally 98% ferrite and 2% austenite.
Learning by Doing (and "cya")
Good record keeping means photocopying a bunch of diagrams and every time you confront the martensite
issue you make a record of how you calculated the nickel and chromium equivalents. You plot these on the
graph, draw the lines between and estimate an adjustment for nitrogen. You note the ferrite number and whether
the bend test is pass or fail.
You don't just do the exercise for samples that fail the bend test. Otherwise you won't learn the limits for welds
that pass every time! If testing the weld for its ferrite number is worthwhile then making the record is also
worthwhile. The day will come when you note the manganese is low and you make yourself into a hero when you
predict the need for a little preheat.
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(The WRC-1992 Diagram modified to reflect experience with manganese. Martensite is predicted to form with
composition equivalents below and to the left of the manganese bands. Reprinted from Advanced
Materials&Process, June 1000, p. 75 - click image to enlarge)
There will be discrepancies. When it happens it most likely means that you misjudged the effect of cooling rate,
or you didn't get the chemistry right, or the basic diagram is imperfect!
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Effects on the martensite, pearlite and bainite formation

Effect on the temperature of martensite formation

All alloying elements with the possible exception of Co, lower Ms the temperature of the start of the martensite
formation, as well as Mf, the finish of the martensite formation, i.e. at 100% martensite. For the majority of steels
containing more than 0.50% C, M
f
lies below room temperature.
This implies that after hardening these steels practically always contain some residual austenite. Ms may be
calculated from the equation given below, by inserting the percentage concentration of each alloying element in
the appropriate term. The equation is valid only if all the alloying elements are completely dissolved in the
austenite.
M
s
= 561 - 474C - 33Mn - 17Ni - 17Cr - 21Mo
For high-alloy and medium-alloy steels Stuhlmann has suggested the following equation:
M
s
(°C) = 550 - 350C - 40Mn - 20Cr - 10Mo - 17Ni - 8W - 35V - 10Cu + 15Co + 30Al
It can be noted that carbon has the strongest influence on the M
s
temperature. Figures 1 and 2 show diagrams
with an example of experimental results of the effect of Mn and Ni on the Ms temperature of various types of
steel.

Figure 1. Effect of Mn on the Ms - temperature (after Russel and McGuire,
Payson and Savage, Zyuzin, Grange and Stewart)
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Figure 2. Effect of Ni on the Ms - temperature (after Russel and McGuire,
Payson and Savage, Zyuzin, Grange and Stewart)

Effect on the formation of pearlite and bainite during the isothermal transformation

All alloying elements except Co delay the formation of ferrite and cementite. It is very difficult to formulate any
general rules regarding the influence exerted by the various alloying elements. However, it has definitely been
found that some elements affect the bainite transformation more than the pearlite transformation, while other
elements act in the opposite manner.

Certain elements will, paradoxically, accelerate the transformations if their concentration increases beyond a
certain limiting value, this limit been affected by other alloying elements present. For case-hardening and tool
steels the time taken to initiate the pearlite-bainite transformation is reduced as the carbon content exceeds
about 1%. For tool steels and constructional steels Si-concentrations of 1,5% and above have been found to
promote pearlite formation.

As a general principle it may be stated that by increasing the concentration of one alloying element by some few
percent and the basic carbon content being kept about 0.50%, only a relatively small retardation of the
transformation rates is noticed. For plain carbon steels a successive increase in C from 0.30% to 1% produces
but a negligible effect. It is only in conjunction with several alloying elements that a more noticeable effect is
produced.

The diagram in Figure 3, applicable to steel W 1 (l% C) will serve as a basis for this discussion. The shortest
transformation time for this steel is less than 1/8th second. Note that the time scale is logarithmic; hence there is
no zero time. As has been mentioned previously, both pearlite and bainite form simultaneously in this steel at
about 550°C. Since the curves overlap it is customary to draw only one curve. With increasing contents of certain
alloying elements, however, the noses of the pearlite and bainite curves will separate.

The structures shown in Figure 3 are obtained by austenitizing samples of steel W 1 at 780°C for 10 min and
quenching in a salt bath at various temperatures. After holding them for predetermined times at various
temperatures they are finally quenched in water. Before the salt-bath quenching the steel contains undissolved
carbides but in view of the composition of the austenite the steel may be regarded as an eutectoid one. The
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diagram should be studied with the aid of the explanatory text below.


Figure 3. TTT diagram for isothermal transformation of steel W 1 (1% C)
A = austenite, B = bainite,
Ms = start of martensite transformation,
M50 = 50% M, P = pearlite
1. Quenching in a liquid bath at 700°C; holding time 4 min. During this interval the C has separated out,
partly as pearlite lamellae and partly as spheroidized cementite. Hardness 225 HV.
2. Quenching to 575°C, holding time 4 s. A very fine, closely spaced pearlite as well as some bainite has
formed. Note that the amount of spheroidized cementite is much less than in the preceding case.
Hardness 380 HV.
3. Quenching to 450°C, holding time 60 s. The structure consists mainly of bainite. Hardness 410 HV.
4. Quenching to 20°C (room temperature). The matrix consists of, roughly, 93% martensite and 7%
retained austenite. There is some 5% cementite as well which has not been included in the matrix figure.
Hardness 850 HV.


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Steel Alloys

Below is a list of some SAE-AISI designations for Steel (the xx in the last two digits indicate the carbon
content in hundredths of a percent)
Carbon Steels
10xx Plain Carbon
11xx Resulfurized
12xx Resulfurized and rephosphorized
Manganese steels
13xx Mn 1.75
Nickel steels
23xx Ni 3.5
25xx Ni 5.0
Nickel Chromium Steels
31xx Ni 1.25 Cr 0.65-0.80
32xx Ni 1.75 Cr 1.07
33xx Ni 3.50 Cr 1.50-1.57
34xx Ni 3.00 Cr 0.77
Chromium Molybdenum
steels

41xx Cr 0.50-0.95 Mo 0.12-0.30
Nickel Chromium
Molybdenum steels

43xx Ni 1.82 Cr 0.50-0.80 Mo 0.25
47xx Ni 1.05 Cr 0.45 Mo 0.20 – 0.35
86xx Ni 0.55 Cr 0.50 Mo 0.20
Nickel Molybdenum
steels

46xx Ni 0.85-1.82 Mo 0.20
48xx Ni 3.50 Mo 0.25
Chromium steels
50xx Cr 0.27- 0.65
51xx Cr 0.80 – 1.05
Illustration of effect of Carbon content on
Steel Hardness

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Carbon Steel to Austenitic Steel

When a weld is made using a filler wire or consumable, there is a mixture in the weld consisting of approximately
20% parent metal and 80% filler metal alloy ( percentage depends on welding process, type of joint and welding
parameters).
Any reduction in alloy content of 304 / 316 type austenitic is likely to cause the formation of martensite on
cooling. This could lead to cracking problems and poor ductility. To avoid this problem an over alloyed filler
metal is used, such as a 309, which should still form austenite on cooling providing dilution is not excessive.
The Shaeffler diagram can be used to determine the type of microstructure that can be expected when a filler
metal and parent metal of differing compositions are mixed together in a weld.
The Shaeffler Diagram


The Nickel and other elements that form Austenite, are plotted against Chrome and other elements that form
ferrite, using the following formula:-
Nickel Equivalent = %Ni + 30%C + 0.5%Mn
Chrome Equivalent = %Cr + Mo + 1.5%Si + 0.5%Nb
Example, a typical 304L = 18.2%Cr, 10.1%Ni, 1.2%Mn, 0.4%Si, 0.02%C
Ni Equiv = 10.1 + 30 x 0.02 + 0.5 x 1.2 = 11.3
Cr Equiv = 18.2 + 0 + 1.5 x 0.4 + 0 = 18.8
A typical 309L welding consumable Ni Equiv = 14.35, Cr Equiv = 24.9
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The main disadvantage with this diagram is that it does not represent Nitrogen, which is a very strong Austenite
former.
Ferrite Number
The ferrite number uses magnetic attraction as a means of measuring the proportion of delta ferrite
present. The ferrite number is plotted on a modified Shaeffler diagram, the Delong Diagram. The Chrome and
Nickel equivalent is the same as that used for the Shaeffler diagram, except that the Nickel equivalent includes
the addition of 30 times the Nitrogen content.


Examples


The Shaeffler diagram above illustrates a carbon steel C.S , welded with 304L filler. Point A represents the
anticipated composition of the weld metal, if it consists of a mixture of filler metal and 25% parent metal. This
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diluted weld, according to the diagram, will contain martensite. This problem can be overcome if a higher
alloyed filler is used, such as a 309L, which has a higher nickel and chrome equivalent that will tend to pull point
A into the austenite region.
If the welds molten pool spans two different metals the process becomes more complicated. First plot both
parent metals on the shaeffler diagram and connect them with a line. If both parent metals are diluted by the
same amount, plot a false point B on the diagram midway between them. (Point B represents the microstructure
of the weld if no filler metal was applied.)


Next, plot the consumable on the diagram, which for this example is a 309L. Draw a line from this point to false
point B and mark a point A along its length equivalent to the total weld dilution. This point will give the
approximate microstructure of the weld metal. The diagram below illustrates 25% total weld dilution at point A,
which predicts a good microstructure of Austenite with a little ferrite.

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The presence of martensite can be detected by subjecting a macro section to a hardness survey, high hardness
levels indicate martensite. Alternatively the weld can be subjected to a bend test ( a side bend is required by the
ASME code for corrosion resistant overlays), any martensite present will tend to cause the test piece to break
rather than bend.
However the presence of martensite is unlikely to cause hydrogen cracking, as any hydrogen evolved during the
welding process will be absorbed by the austenitic filler metal.

More reading:
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Selection of Age-Hardenable Superalloys

By Richard B. Frank
High-Temperature R&D
Carpenter Technology Corp., Reading, PA, USA
Superalloys are high-performance materials designed to provide high mechanical strength and resistance to
surface degradation at high temperatures of 1200°F (650°C) or above. They combine high tensile, creep-rupture,
and fatigue strength; good ductility and toughness, with excellent resistance to oxidation and hot corrosion.
Furthermore, superalloys are designed to retain these properties during long-term exposures at the elevated
temperatures.
This article focuses on the wrought age-hardenable alloys, which are the most commonly used superalloys.
Wrought materials can be formed using hot and cold working operations. Not discussed here are the cast,
powder (P/M), and oxide dispersion strengthened (ODS) superalloys that can also offer enhanced properties.
The first age-hardenable, high-temperature alloy dates back to about 1929 when various developers added
titanium and aluminum to the standard 80% nickel/20% chromium resistance wire alloy. This was a precursor to
the 80A nickel-base superalloy, developed in 1940-1944, but still in use today.
Little was done to advance the original age-hardenable alloys until the time period of 1935-1944 when World
War II spurred demand for improved alloys that could be used in the early aircraft gas turbine engines. Alloy
development activity exploded in the 1950’s and 1960’s to keep pace with the demands of the gas turbine engine
industry. Progress in superalloy development not only made the jet engine possible, but allowed for constantly
increasing thrust-to-weight ratios over the last 60 years.
Applications
The primary application for superalloys is still in hot sections of aircraft gas turbine engines, accounting for over
50% of the weight of advanced engines. However, the excellent performance of these materials at elevated
temperatures has expanded their application far beyond one industry.
In addition to the aerospace industry, these alloys are used in turbine engines for marine, industrial, land-based
power generation, and vehicular applications. Specific engine parts using superalloys include turbine discs,
blades, compressor wheels, shafts, combustor cans, afterburner parts and engine bolts.
Beyond the gas turbine engine industries, superalloys are commonly used for applications in rocket engines,
space, petrochemical/energy production, internal combustion engines, metal forming (hot-working tools and
dies), heat-treating equipment, nuclear power reactors, and coal conversion.
While these alloys are primarily used for service at elevated temperatures above 1000°F (540°C), the
characteristics of high strength and excellent environmental resistance have made some superalloys an
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excellent choice for lower-temperature applications. Examples are prosthetic devices in the medical industry and
components for deep sour gas wells in the oil/gas exploration industry.
Chemical Composition
Table 1 contains the nominal compositions of the most common wrought age-hardenable superalloys. These
alloys contain various combinations of nickel, iron, cobalt, and chromium with lesser amounts of other elements
including molybdenum, niobium, titanium, and aluminum. With minor additions of beneficial elements such as
boron and zirconium, these alloys may contain up to 12 intentional additions. All these additions help to impart
and maintain the desired properties at elevated temperatures.

Many other elements such as silicon, phosphorus, sulfur, oxygen, nitrogen and a larger number of tramp
elements (like lead, bismuth, selenium) must be tightly controlled in superalloys to avoid detrimental effects on
high-temperature properties. These minor and tramp elements are controlled during raw material selection prior
to melting, as well as during the melting/remelting processes.
Superalloys can be classified into nickel-base, iron-base, and cobalt-based groups. Nickel-based superalloys
(>50% Ni) are the most common group. About half of the alloys in Table 1 are considered nickel-base alloys and
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the others contain large additions of nickel. The nickel base has a high tolerance for alloy additions that might
otherwise cause phase instability leading to loss of strength, ductility, and/or environmental resistance.
Iron-based superalloys are less costly, but are less tolerant of alloying additions and typically have lower
mechanical properties and maximum temperature limitations. Examples are Pyromet® Alloy A-286 and NCF
3015 (Ni-30) alloy. These alloys contain an austenitic stainless steel base with additions of nickel, titanium, and
aluminum to promote age hardening. Pyromet Alloy 706 and Pyromet Alloy 901 have similar amounts of nickel
and iron and can be considered nickel-iron-base superalloys. The higher nickel levels of 901 and 706 alloys
allow for larger additions of strengthening elements without undesirable effects.
Although there are some cobalt-base superalloys, they are significantly higher in cost and typically cannot be
age hardened to high strength levels. However, cobalt is an important alloying addition to nickel-based alloys
because it extends the maximum temperature for usage by reducing the solubility of the age-hardening phase.
Waspaloy and Pyromet Alloy 41 and Pyromet Alloy 720 are nickel-base alloys with 10-15% cobalt additions.
These alloys have the highest temperature capability of the common wrought age-hardenable superalloys.
Chromium, usually in the range of 14 to 23 weight percent, is a critical alloying addition to nearly all superalloys.
As in stainless steels, chromium forms a tightly-adherent, protective oxide film (Cr
2
O
3
) on the alloy surface to
resist oxidation and corrosion at high temperatures as well as corrosion at lower temperatures. This surface layer
protects the alloy from the harmful effects of the elements oxygen, nitrogen, and sulfur.
Although most superalloys contain at least 14% chromium, in some applications, it is critical to minimize thermal
expansion. Pyromet CTX-909 and Thermo-Span® alloys are considered low-expansion superalloys that have
low chromium contents to minimize expansion of the nickel-cobalt-iron base. Resistance to oxidation and hot
corrosion are reduced so high-temperature coatings are often applied prior to service. Of the two alloys, 909
alloy provides the lowest expansion coefficient while Thermo-Span alloy (5.5% chromium) provides improved
environmental resistance.
Refractory elements like molybdenum, tungsten, and niobium, with their large atomic diameters, increase high
temperature strength and stiffness by straining the nickel/iron base matrix. Alloys 901 and 41 contain larger
additions of molybdenum to increase this solid solution strengthening effect. Other alloying additions such as
chromium and aluminum also contribute to solid solution strengthening but to a lesser extent.
The elements titanium, aluminum, and niobium are added to the nickel or nickel-iron matrix to form an
intermetallic Ni
3
(Al, Ti, Nb) phase during age-hardening heat treatments. The resultant gamma prime or gamma
double prime phases are the primary strengthening agents in superalloys. This will be discussed in more detail in
the next section on age-hardening.
Although elements such as boron, zirconium, and magnesium may be added at levels less than 0.1 weight
percent, the beneficial effects can be very potent. These elements segregate to and stabilize grain boundaries,
which significantly improves hot workability, high temperature strength and ductility. Small additions of carbon
also may be added to form carbides that restrict grain growth and grain boundary sliding during high temperature
exposure.
Age-Hardening
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The major strengthening method in superalloys is age-hardening. Yield strength of nickel alloys is typically
increased by a factor of two or three by precipitation of the gamma prime and/or gamma double prime, Ni
3
(Al, Ti,
Nb) hardening phase. Although the phase is based on the nickel aluminide (Ni
3
Al) intermetallic, up to 60% of the
aluminum can be replaced by titanium or niobium, which actually increases strength of the alloy.
The gamma prime phase is rather unique in that its strength actually increases with temperature up to 1200°F
(650°C) and it is relatively ductile and resistant to oxidation. Gamma prime precipitates as very fine spheroidal or
cuboidal particles in the nickel-iron matrix during aging.
While most of the superalloys employ the titanium-rich gamma prime phase for age hardening, a niobium-rich
variant called gamma double prime is the primary strengthening phase in some superalloys such as Pyromet
Alloy 706 and Pyromet Alloy 718. The niobium-rich phase provides higher strength up to 1200°F (650°C) but is
unstable above 1200°F. Thus, 706 and 718 alloys have a lower temperature limit than the alloys strengthened
with the titanium-rich gamma prime phase. Since the gamma double prime reaction is more sluggish, these
alloys also tend to have better hot workability and weldability.
Heat Treatment
Proper heat treatment is critical to achieving the desired level of properties in age-hardenable superalloys.
Typical heat treatments for these alloys are listed in the mechanical property Tables 2 and 3. The initial solution
heat treatment typically dissolves all precipitated phases except for some primary carbide and nitride phases.
The typical range for the wrought age-hardenable superalloys is 1650-2100°F (900-1150°C) for 1 to 4 hours
followed by a rapid air cool or a quench in water, polymer or oil.
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The selection of solution treatment time and temperature varies with the alloy and its phase solvus temperatures,
and also depends on the specific properties that are most important for the intended application. Alloys with
higher hardener contents (Ti, Al, Nb) require higher temperatures to solution any hardener phase that may have
precipitated during hot working or cooling. Best tensile and fatigue properties are typically obtained with lower
solution temperatures that result in a finer grain size. In contrast, better long-term stress-rupture and creep
properties are generally obtained with higher-temperature solution treatments that result in coarser grain size
and lower tensile yield strength. For these reasons, it is common to specify two or more preferred heat
treatments for superalloys.
In some cases, another objective of the solution treatment is to form a desirable distribution of a second phase
such as carbide in Pyromet 41 alloy and delta phase (Ni
3
Nb) in Pyromet 718 alloy. After solution treatment, one
or more aging treatments are applied to precipitate the hardening phase and possibly other phases in the
desired amount and distribution. As with solution treatment, the selection of aging temperatures is dependent on
the alloy and the combination of properties desired.
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The aging range for age-hardenable superalloys is 1150-1600°F (620-870°C). Aging times range from 4 hours to
24 hours. Double-aging treatments are quite common to maximize strength and to develop the best combination
of short-term tensile and long-term creep-rupture properties. The primary aging treatment precipitates a coarser
distribution of the hardener phase and may also improve the type and distribution of carbides on grain
boundaries.
The secondary age is typically about 200°F below the primary aging temperature, precipitating a finer dispersion
of the gamma prime phase. For some higher-strength applications, the alloy is direct aged after hot, warm, or
cold working without an intermediate solution treatment. The strain from working is used to further enhance
tensile and fatigue properties with some sacrifice in creep-rupture properties.
Mechanical Properties
For the design engineer or materials specifier, a review of terms defining applicable mechanical properties may
be helpful:
Tensile Properties – The design of load-bearing structures is often based on yield strength or, in some cases,
the ultimate tensile strength of the material. Yield strength is a measure of the maximum stress a material can
withstand before it permanently deforms. Tensile strength is a measure of the maximum stress a material can
withstand before it fractures. Elevated temperature tensile properties are most applicable to short-time
exposures at higher temperatures. Creep and stress-rupture properties are more applicable for longer
exposures.
Creep and Rupture Properties – Creep and rupture strengths become important when the material must
withstand the combined effects of high temperature and stress for long periods of time. At elevated temperatures,
metals will stretch or "creep" at stresses well below the yield strength. Superalloys are more resistant to creep
than low-alloy or stainless steels, but creep will still occur above about 1000°F (540°C). Creep properties are a
measure of the alloy’s resistance to stretching under a constant load. Stress-rupture or creep-rupture properties
are a measure of resistance to fracture under a constant load (creep test taken to fracture). Both properties are
expressed as stress or strength values that will cause a given amount of creep (0.1%-1%) or rupture in a given
amount of time (100 to 100,000 hours).
Tables 2 and 3 list typical tensile (yield) and stress-rupture strength properties of the age-hardenable superalloys
at temperatures of 1200-1600°F (650-870°C). Yield strengths at room temperature are also listed in Table 2.
These properties are shown graphically in Figures 1 and 2. It should be noted that the data represents
approximate nominal strength values for specific heat treatments. Actual values can vary by up to 35% due to
differences in composition, hot/cold working practices, and heat treatment.
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For example, superalloys like Pyromet 718 and Waspaloy may contain several different aim compositions within
the broader industry ranges to optimize properties for specific applications. Higher levels of the age-hardening
elements titanium, aluminum, and niobium result in higher strength. Hot or cold working an alloy to obtain a finer
grain size typically increases tensile yield strength but decreases stress-rupture strength.
As discussed previously, properties of all age-hardenable superalloys are dependent on heat treatment. Alloys
like Pyromet Alloy X-750 and Waspaloy have two or more preferred heat treatments (see Table 2) depending on
whether the application requires better short-time tensile and fatigue properties or long-time creep and
stress-rupture properties. Examples of alternative heat treatments have been shown for Waspaloy and X-750
alloys but the reader should refer to manufacturers’ datasheets for a more complete listing of alternative heat
treatments for the other superalloys.
Other Properties – While tensile and creep-rupture are the most basic mechanical properties considered for
high-temperature applications, design criteria may also consider resistance to fatigue (low- and high-cycle),
crack growth, and wear/erosion. Hardness and hot hardness tests are sometimes used as a rough measure of
yield strength and wear/erosion.
Alloy Selection
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A simplified method known as the Carpenter Selectaloy® system can help designers and engineers select the
most suitable superalloy based on strength and maximum temperature requirements. Figures 3 and 4 contain
Selectaloy diagrams for the 15 superalloys discussed in this article. Yield strength (Figure 3) or stress-rupture
strength (Figure 4) increases vertically on the Selectaloy diagram, and temperature increases from left to right.
The alloys are shown multiple times on the diagrams since the alloys are useful over a range of temperatures.
The diagram can be used to estimate how the strength of an alloy decreases with temperature, but also how the
strength of different alloys compare at different temperatures.

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It should be noted that the alloys were positioned on the Selectaloy diagrams based on average strength values
representative of compositions and heat treatments commonly used for each alloy. An alloy’s relative position
could move up or down, left or right, with relatively minor modifications of composition, processing and heat
treatment. Temperature limits should be considered approximate. Therefore, while the Selectaloy diagrams are
useful tools to screen candidate alloys, they are not a substitute for a more detailed evaluation of the critical
properties required for an intended application.

Pyromet A-286 alloy is the most basic age-hardenable superalloy in terms of properties and cost. A-286 provides
the lowest strength levels, but still higher by a factor of two than other non-age-hardenable stainless alloys.
When increased strength or temperature resistance is required, higher nickel alloys are typically preferred. Alloys
with the highest levels of strength and temperature resistance typically contain the highest alloy contents and
significant levels of cobalt. Relative cost of these alloys will be discussed in the next section.
The Selectaloy diagrams presented in this article provide a method to compare basic strength properties and
temperature limitations of common wrought age-hardenable superalloys. However, alloy selection will
undoubtedly depend on many other considerations, including other physical and mechanical properties as well
as environmental resistance and cost. For example, Thermo-Span and Pyromet CTX-909 alloys provide a
benefit of much lower expansion during heating but at the expense of oxidation and corrosion resistance in the
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uncoated condition. Pyromet 31V and Pyromet 751 alloys provide similar strength and temperature resistance,
but the higher chromium content of 31V alloy results in much improved resistance to sulfidation and other forms
of hot corrosion.
Alloy Cost
From the user’s standpoint, alloy selection must be based on expected cost effectiveness.
In today’s competitive global environment, overdesign is less common. The trend is to select the lowest-cost
material to meet design requirements for the application. However, a higher-cost alloy may be justified to
minimize overall life cycle cost or for longer service of certain components in a system that is critical or too
expensive to be shut down for maintenance. Surely, knowledge of alloy capabilities is critical in making the best
decision.
As temperature and strength requirements increase, so does the necessary alloy content. Figure 5 compares the
relative alloying costs of the 14 alloys using Pyromet A-286 alloy as a base (cost factor of 1.0). The cost factors
are based on 10-year averages of the intrinsic alloying element costs at market prices. Higher temperature
strength and resistance typically require higher nickel and cobalt contents. Nickel and cobalt prices have
historically been volatile, with high and low prices varying by a factor of 4 to 5. More recently, the price of
molybdenum, a potent solid solution strengthener, has increased in price by a factor of nearly ten over the last
two years.

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As discussed above, the cost factors in Figure 5 are based only on raw material elemental costs (10-year
averages) that fluctuate significantly with time. Differences in melting, working, and other processing costs,
which can be substantial, are not included in these factors. Processing yields and specific end user requirements
(grain size, ultrasonic testing, etc.) significantly impact product cost. However, the cost comparisons are useful
because alloying costs typically represent a large portion of superalloy product cost. Since superalloys are
designed for high temperature strength and resistance to deformation, processing difficulty and cost also
increase with hot strength and maximum temperature capability.
Figure 6 shows the relationships of stress-rupture strength at 1200-1500°F (650-815°C) with raw material cost
factor. It is apparent that the alloys that provide higher levels of strength, temperature resistance, and/or
specialized properties also cost more, which reinforces the importance of the alloy selection process.

More Technical Article:
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Metallurgy of Mo in Alloy Steel & Iron


Spherical Agglomerates of Mo powder (lacy appearance), with solid spheres of the Ni-Cr alloy binder for the Mo powder
Molybdenum metal is usually produced by powder metallurgy techniques in which Mo powder is hydrostratically
compacted and sintered at about 2100°C. Hot working is done in the 870-1260°C range. Moly forms a volatile
oxide when heated in air above about 600°C and therefore high temperature applications are limited to
non-oxidizing or vacuum environments.
Moly alloys have excellent strength and mechanical stability at high temperatures (up to 1900°C). Their high
ductility and toughness provide a greater tolerance for imperfections and brittle fracture than ceramics.

High temperature furnace with molybdenum hot zone (Courtesy of PLANSEE AG, Austria)
The unique properties of molybdenum alloys are utilised in many applications:
• High temperature heating elements, radiation shields, extrusions, forging dies, etc;
• Rotating X-ray anodes used in clinical diagnostics;
• Glass melting furnace electrodes and components that are resistant to molten glass;
• Heat sinks with thermal expansivity matching silicon for semiconductor chip mounts;
• Sputtered layers, only Ångstroms (10
-7
mm) thick, for gates and interconnects on integrated circuit
chips;
• Sprayed coatings on automotive piston rings and machine components to reduce friction and
improve wear.
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For specialised applications, Mo is alloyed with many other metals:
• Mo-tungsten alloys are noted for exceptional resistance to molten zinc;
• Mo is clad with copper to provide low expansion and high conductivity electronic circuit boards;
• Mo-25% rhenium alloys are used for rocket engine components and liquid metal heat exchangers
which must be ductile at room temperature.
Hardening
The purpose of quenching steel after heating is hardening, i.e. to produce a hardened microstructure over the
full cross section of the workpiece.
A round steel bar quenched in water from a temperature up to 900°C will cool faster near the surface than in the
center (Fig 2 below).

Fig 2: Quenching round bar

Fig 3: Simulating cooling of steel sections

On a laboratory scale this is simulated by the Jominy end quench test (Fig 3 above).
The standard sample is heated and then water quenched on one end. The cooling rate in the sample decreases
from the water sprayed end where it is highest to the opposite end where it is lowest. When the sample is cool,
the surface is ground and the hardness profile is taken. The change of hardness along the sample reflect
variations of the microstructure brought about by the different cooling rates.
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The curves in Fig 4 compare the hardness profile of steels with different alloy contents. The carbon manganese
steel without molybdenum has only been hardened near the quenched end of the sample and the hardness
drops quickly when moving away from the quenched end. With increasing molybdenum content the hard
microstructure is maintained at increasing distances from the quenched end. That means that it is possible to
harden a steel with higher molybdenum content with slower cooling rates: the hardenability is improved.

Fig 4: Jominy hardenability curves: Hardenability improves with increasing Mo content (after W.W. Cias
1
)
The hardenability indicates the depth, to which a steel grade can be hardened.
In standard Quenched and Tempered Steels a combination of alloying elements is usually used, including
manganese, chromium, molybdenum, nickel and silicon.
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Fig 5: The Hardenability Multiplying Factor shows the rate at which the hardening depth is increased with the percentage of
the alloying element (after Honeycombe
2
)
The basis of steel hardening lies in the fact, that iron exists in two crystal structures:
Below 912°C and from 1394°C to its melting point iron is body centered cubic – bcc – called ferrite. In the lower
temperature range ferrite is also referred to as alpha iron, in the higher temperature range as delta iron.
At a temperatures from 912°C to 1394°C iron is in the face centered cubic crystal structure – fcc – called gamma
iron or austenite. Heating pure iron above 912°C transforms the structure from Ferrite into Austenite. Cooling
the iron from the austenitizing area below 912°C results in the original bcc iron structure, no matter what cooling
rate is applied.
Pure iron can not be hardened.
The addition of carbon converts iron into hardenable steel. (Alloying elements such as manganese, molybdenum
and chromium enhance the hardenability).
Carbon is present in iron both in solid solution and in the form of carbides. It is significant that the sides of the
face centered cubes of the austenite are about 25% larger than the sides of the body centered cube of the ferrite.
The solubility for carbon is therefore much greater in austenite than in ferrite.
When a steel with say 0.4% carbon is heated above the ferrite.austenite (alpha-gamma) transformation point,
carbon and the other alloying elements can go into solid solution in the spacious austenitic fcc
structure. Subsequent cooling through the gamma – alpha transformation point leads into the narrow ferrite
structure. There is not enough space in this structure to keep carbon in solid solution.
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So, if the cooling rate is low, carbide is formed in connection with the transformation process. As a result the
microstructure at room temperature consists of ferrite and carbide. (The fine lamellar structure of ferrite and iron
carbide is called pearlite - see Fig 6).

Fig 6: Ferrite – Pearlite microstructure – soft and ductile

Fig 7: Martensite microstructure –hard and brittle
The critical factor is, that there is enough time available for the carbon atoms to move through the lattices to form
carbides, which results in the soft microstructure of ferrite and pearlite.
Increasing the cooling rate progressively reduces the carbide formation. A very high cooling rate is achieved
with water quenching, which completely supresses the carbide formation. In that case carbon is uncomfortably
forced into narrow spaces in the ferrite structure. The microstructure which is generated that way is called
martensite. This is the hardest and most brittle form of steel. (See Fig 7)
In plain carbon steels the high cooling rates required for the formation of martensite are only achieved near the
quenched surface. Inside the work piece the structure remains soft. Water quenching larger sections also
involves the risk of quench cracking.
This is where molybdenum and the other alloying elements enter the scene. Alloying elements slow down the
diffusion of carbon atoms through the iron lattice., which delays the transformation from austenite into
ferrite. The hardenability of the steel is thus improved since martensite can be produced at slower cooling
rates. As shown in Fig 5, molybdenum is very effective in that respect.
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Also, in larger cross sections at intermediate cooling rates a structure called Bainite is formed particularly in Mo
alloyed steel. In that case, some nucleation of carbides has taken place during cooling before the austenite-
ferrite transformation.
In practice, the microstructure of quenched and tempered steel components consists of a combination of
martensite and bainite.
Tempering
Hardened steel must be tempered, i.e. reheated for two reasons:
• Different cooling rates between edge and core of components result in internal stresses, which
must be relieved.
• High hardness martensite and bainite must be softened to avoid brittle cracking.
The improvement of ductility is inevitably accompanied by softening, i.e. a loss of strength. This is very
pronounced with carbon steel. An important function of alloying elements is to delay temper softening.
Through its capability of forming carbides, molybdenum, carefully combined with chromium and vanadium, is
very efficient in delaying the loss of strength during tempering while improving fracture toughness. The resulting
structure, tempered martensite, is very strong with an acceptable level of toughness.
Fig 8 shows the effect of molybdenum on the hardness after tempering of a 0.35% carbon steel. It significantly
delays softening of the steel. At sufficiently high Mo contents the hardness curve may even increase with
increasing tempering temperature. This is known as secondary hardening.
The effect of secondary hardening on tempering is an important function of molybdenum in high speed steels
and in some tool- and die steels.
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Fig 8: Influence of Mo content on temper softening (after E.C. Bain
3
)
Temper brittleness
Temper embrittlement may occur when steels are slowly cooled after tempering through the temperature range
between 450 and 550°C. This is due to the segregation of impurities such as phosphorus, arsenic, antimony
and tin on the grain boundaries. The molybdenum atom is very large relative to other alloying elements and
impurities. It effectively impedes the migration of those elements and thereby provides resistance to temper
embrittlement.
Fig 9 shows the ductile-to-brittle transition temperature for two steels. This temperature is an indication for the
lower limit of the service temperature without the risk of brittle failure.
If the steels are water quenched after tempering, both steels one without molybdenum and one with 0.15%
molybdenum, have essentially the same ductile to brittle behaviour (transition at approx. -50°C). However, if the
steels are slowly cooled in the furnace after tempering the picture changes. The transition to brittle fracture has
shifted to +25°C for the Cr-steel, while it remained at -50°C for the Cr-Mo steel. The slow cooling rate has not
embrittled the molybdenum containing steel, it is, therefore, less susceptible to temper embrittlement.
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Fig 9: Ductile to brittle transition for two tempered steels, as a function of cooling rate after tempering (after Dunn et al
4
)
Hydrogen embrittlement and sulphide stress cracking
As outlined above, the strength levels obtained in quenched and tempered steels are based mainly on the high
strength of martensite, a microstructure characterized by a high density of dislocations and high internal
stresses.
Unfortunately, exactly these conditions enhance the diffusion of hydrogen into steel and cause hydrogen
embrittlement. Tempering reduces the internal stresses and the dislocation density of martensite, hence
reduces hydrogen diffusion. However, the strength can be lowered to insufficient levels. Molybdenum is efficient
in mittigating this effect in two ways: through solid solution strengthening and the formation of complex carbides
together with other elements such as chromium and niobium.
In cases, where hydrogen sulphide is the source of the hydrogen the phenomenon is called sulphide stress
cracking (SCC). The capability of molybdenum to provide resistance to sulphide stress cracking has been the
key to the development of a broad range of steel grades used for Oil Country Tubular Goods and in chemical and
petrochemical plants.

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High temperature hydrogen attack

Carbon steel has severe limitations at conditions of hydrogen attack above about 200 C as are common in
processes such as petroleum distilling and catalytic reforming. The hydrogen diffusing into the steel
combines with carbon present to form methane and other products. The result is first decarburization and
subsequently fissuring due to high gas pressure at localized sites.
Fig. 10 below compares the loss of rupture strength of various steels exposed to pressurized hydrogen at 540 C:
• the unalloyed carbon steel has obviously suffered the damage described above, loosing more tha
50 % of it’s original strength after less tha 50 hours exposure,
• additions of 0.5% Mo or 1%Cr-0.5%Mo show a slight improvement, but are not adequate under the
given conditions, whereas
• the alloy content of 2.25%Cr plus 1% Mo provide protection to the extent, that after 500 hours
exposure the original rupture strength of the steel has not deteriorated at all.

Fig. 10: Effect of composition and exposure time on the strength of steels exposed to hydrogen at 63 bar at 540 C. The
strength of samples exposed in argon is taken as 100%. (After Nelson
5
)
The positive effect of Cr plus Mo in this context used to be described as carbide forming and is now referred to as
elements lowering grain boundary energy. In any event with suitable selection of Mo and Cr contents the steel
will be resistant to hydrogen attack in respect to decarburization, fissuring and loss of strength (4; page 65ff).
http://www.imoa.info/moly_uses/moly_grade_alloy_steels_irons/hardening.html
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Maraging Steels


Maraging steel

Al/maraging steel fibre composite prepared via vacuum diffusion bonding of
plasma sprayed monolayers


Maraging steels are carbon free iron-nickel alloys with additions of cobalt, molybdenum, titanium and
aluminium. The term maraging is derived from the strengthening mechanism, which is transforming the alloy to
martensite with subsequent age hardening. Air cooling the alloy to room temperature from 820°C creates a soft
iron nickel martensite, which contains molybdenum and cobalt in supersaturated solid solution. Tempering at
480°C to 500°C results in strong hardening due to the precipitation of a number of intermetallic phases, including,
nickel-molybdenum, iron-molybdenum and iron-nickel varieties.

ƒ Age harden carbon free martensitic steel
ƒ Principle alloying element Nickel.
ƒ Precipitates hardening
ƒ Secondary alloying elements: Mo, Al, Cu, Ti, Ni and Co
ƒ Intermetallic precipitates such as Ni3Ti and Ni3Mo on age hardening at about 500°C.
Introduction:

The 18% Ni-maraging steels, which belong to the family of iron-base alloys, are strengthened by a process of
martensitic transformation, followed by age or precipitation hardening. Precipitation hardenable stainless steels
are also in this group. Maraging steels work well in electro-mechanical components where ultra-high strength is
required, along with good dimensional stability during heat treatment. Several desirable properties of maraging
steels are:
The result is steel which:
• Possesses high strength and toughness.
• Allows for easy machining with minimal distortion.
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• Has uniform, predictable shrinkage during heat treatment which results in minimum distortion
• Can be easily nitrided.
• Resists corrosion and crack propagation.
• Superior fracture toughness compared to quenched and tempered steel of similar strength level
• Low carbon content, which precludes decarburization problems
• Section size is an important factor in the hardening process
• Easily fabricated
• Can be finely polished.
• Good weldability.
These factors indicate that maraging steels could be used in applications such as shafts, and substitute for long,
thin, carburized or nitrided parts, and components subject to impact fatigue, such as print hammers or clutches.
Maraging steels (from Martensitic Aging) are iron alloys which are known for possessing superior strength
without losing malleability. The iron base is alloyed principally with a large percentage of nickel to produce a very
specific heat-treatment product. Other alloying elements include molybdenum, aluminum, copper and titanium
and are added to produce intermetallic precipitates. Cobalt is added in percentages up to 12% to accelerate the
precipitation reactions and ensure profuse and uniform precipitates. Maraging steel is essentially free of carbon,
which distinguishes it from most other types of steel. These steels are a special class of low carbon ultra-high
strength steels which derive their strength not from carbon, but from precipitation of inter-metallic compounds.
The principal alloying element is 15 to 25% nickel. Secondary alloying elements are added to produce
intermetallic precipitates, which include cobalt, molybdenum, and titanium. Original development was carried out
on 20 and 25% Ni Nickel steels to which small additions of aluminium Al, titanium Ti, and niobium Nb were made.

The common, non-stainless grades contain 17~19% nickel, 8~12% cobalt, 3~5% molybdenum and 0.2~1.6%
titanium. Stainless grades rely on chromium not only to prevent their rusting, but to augment the hardenability of
the alloy as their nickel content is substantially reduced. This is to ensure they can transform to martensite when
heat-treated, as high chromium, high nickel steels are generally austenitic, and unable to undergo such a
transition.

Maraging steels are hardened by a metallurgical reaction that does not involve carbon. These steels are
strengthened by intermetallic compounds such as Ni3Ti and Ni3Mo that precipitate at about 500°C. These steels
typically have very high nickel, cobalt and molybdenum contents while carbon is essentially an impurity and its
concentration is kept as low as possible in order to minimize the formation of titanium carbide which can
adversely affect mechanical properties.

Ultra-high strengths may be obtained with these steels, and weldability is good. Toughness is superior to all low
alloy carbon steels of similar strength, particularly the low temperature toughness. Although they are expensive,
they are easy to machine and heat treat, so that some economies result in component production.

The common, non-stainless grades contain 17~19% nickel, 8~12% cobalt, 3~5% molybdenum, and 0.2~1.6%
titanium. Stainless grades rely on chromium not only to prevent their rusting, but to augment the hardenability of
the alloy as their nickel content is substantially reduced. This is to ensure they can transform to martensite when
heat treated, as high-chromium, high-nickel steels are generally austenitic, and unable to undergo such a
transition.
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Properties:

Due to the low carbon content maraging steels have good machinability. Prior to aging, they may also be cold
rolled to as much as 80~90% without cracking. Maraging steels offer good weldability, but must be aged
afterward to restore the properties of heat affected zone.

When heat treated the alloy has very little dimensional change, so it is often machined to its final dimensions.
Due to the high alloy content the alloys have a high hardenability. Since ductile FeNi martensites are formed
upon cooling, cracks are non-existent or negligible. They can also be nitrided to increase case hardness. They
can be polished to a fine surface finish. Non-stainless varieties of maraging steels are moderately corrosion
resistant and resist stress corrosion and hydrogen embrittlement. More corrosion protection can be gained by
cadmium plating or phosphating.


Surface markings due to the formation of martensite plates in Fe-Ni single crystals.
The width of the figure corresponds to 4mm of the sample.

• Offer the best available combination of ultra-high yield and tensile strength, ductility and fracture
toughness of any ferrous materials.
• Can retain strength at least up to 350 °C.
• Being a very low-carbon martensite, the structure is soft. Readily machinable. May be cold rolled to as
much as 80 - 90% without cracking before aging treatment. Hot deformation is also possible.
• Possible to finish-machine before aging. Very little dimensional change after aging treatment.
• Parts uniformly harden throughout the entire section because they have high hardenability.
• Exhibit good weldability. Properties of heat affected zone (HAZ) can be restored by a post-weld aging
treatment.
• Since ductile FeNi martensites are formed upon cooling, cracks are non-existent or negligible.
• Can be surface hardened by nitriding.
• Good corrosion, stress corrosion and hydrogen embrittlement characteristics.
• Protection can be provided by cadmium plating or phosphating.
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Heat Treatment:

Annealing.
The steel is first annealed, at approximately 820 °C for 15 to 30 minutes for thin sections and for 1 hour per 25
mm thickness for heavy sections, to ensure formation of a fully austenitized structure. This is followed by air
cooling to room temperature to form a soft, heavily dislocated iron-nickel lath (untwinned) martensite (hence the
"mar-" in mar-aging). Subsequent aging (precipitation hardening) of the more common commercially used alloys
for ~3 hours in 480-500 °C range produces a fine dispersion of Ni
3
(X,Y) intermetallic phases along dislocations
left by martensitic transformation, where X and Y are solute elements added for such precipitation, eg; Mo, Ti, Al,
Cu, Si. Newer compositions of maraging steels have revealed other intermetallic stoichiometries and
crystallographic relationships with the parent martensite, including rhombohedral and massive complex
Ni
50
(X,Y,Z)
50
- usually simplified to Ni
50
M
50
. Overaging leads to a reduction in stability of the primary, metastable,
coherent precipitates, leading to their dissolution and replacement with semi-coherent Laves phases such as
Fe
2
Ni/Fe
2
Mo. Further excessive heat-treatment brings about the decomposition of the martensite and reversion
to austenite.
Tempering:
Maraging steels are carbonless Fe-Ni alloys additionally alloyed with cobalt, molybdenum, titanium and some
other elements. A typical example is an iron alloy with 17-19% Ni, 7-9% Co, 4.5-5% Mo and 0.6-0.9% Ti. Alloys
of this type are hardened to martensite and then tempered at 480°C~500°C. The tempering results in strong
precipitation hardening owing to the precipitation of intermetallic from the martensite, which is supersaturated
with the alloying elements. By analogy with the precipitation hardening in aluminum, copper and other
non-ferrous alloys, this process has been termed ageing, and since the initial structure is martensite, the steels
have been called maraging.
The structure of commercial maraging steels at the stage of maximum hardening can contain partially coherent
precipitates of intermediate metastable phases Ni
3
Mo and Ni
3
Ti. Of special practical value is the fact that
particles of intermediate intermetallic in maraging steels are extremely disperse, which is mainly due to their
precipitation at dislocations.
The structure of maraging steels has a high density of dislocations, which appear on martensitic rearrangement
of the lattice. In lath (untwined) martensite, the density of dislocations is of an order of 10
11
-10
12
cm
-2
, i.e. the
same as in a strongly strain-hardened metal. In that respect the substructure of maraging steel (as hardened)
differs appreciably from that of aluminum, copper and other alloys which can be quenched without polymorphic
change. (Polymorphism (materials science), the ability of a solid material to exist in more than one form or crystal structure)
It is assumed that the precipitation of intermediate phases on tempering of maraging steels is preceded with
segregation of atoms of alloying elements at dislocations. The atmospheres formed at dislocations serve as
centers for the subsequent concentration stratification of the martensite, which is supersaturated with alloying
elements.
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In maraging steels the dislocation structure that forms in the course of martensitic transformation, is very stable
during the subsequent heating and practically remains unchanged at the optimum temperatures of tempering
(480°C -500°C). Such a high density of dislocations during the whole course of tempering may be due to an
appreciable extent, to dislocation pinning by disperse precipitates.
A long holding in tempering at a higher temperature (550°C or more) may coarsen the precipitates and increase
the inter particle spacing, with the dislocation density being simultaneously reduced. With a long holding time,
semi coherent precipitates of intermediate intermetallic are replaced with coarser incoherent precipitates of
stable phases such as Fe
2
Ni or Fe
2
Mo.
At increased temperatures of tempering (above 500°C), maraging steels may undergo the reverse martensitic
transformation, since the as point is very close to the optimum temperatures of tempering. The formation of
austenite is then accompanied with the dissolution of the intermetallic that has precipitated from the
gamma-phase.
Application:

Maraging steel's strength and malleability in the pre-aged stage allows it to be formed into thinner rocket and
missile skins, allowing more room for payload while still possessing sufficient strength for the application.
Maraging steels have very stable microstructural properties, and even after overaging due to excessive
temperature only soften very sluggishly. These alloys retain their properties at mildly elevated operating
temperatures and have maximum service temperatures of over 400 °C. They are suited to engine component
applications such as crankshafts and gears, that work at 'warm' temperatures, and the firing pins of automatic
weapons that cycle from hot to cool repeatedly while under substantial loads and impacts. Their uniform
expansion and easy machinability, carried out before aging makes maraging steel useful in high wear portions of
assembly lines, as well as in the manufacture of dies. Other ultra-high strength steels, such as the secondary
hardening 'Aermet©' family are not so amenable to processing because of their ever-present carbide particle
dispersion.
In the sport of fencing, testing has shown that the blade breakage patterns in carbon steel and maraging steel
blades are identical. Maraging blades are required in foil and épée (there is no such requirement for sabre
blades) because the crack propagation in maraging steel is 10 times slower than in carbon steel. This results in
less blade breakage and fewer injuries.
Stainless maraging steels have been used in golf club heads and in surgical components and hypodermic
syringes. They are not suitable for scalpel blades, as their virtually zero carbon content prevents holding a good
cutting edge.
Maraging steel is also an item of great interest to those responsible for national security. Maraging steel is used
in creating gas centrifuges for uranium enrichment due to its extremely high strength and balance. Very few other
materials will work for this task, and maraging steel’s other uses are very specialized. Nations importing
maraging steel often find themselves receiving a great deal of attention.
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Physical Properties:

• Density: 8.1 g/cm³ (0.29 lb/in³)
• Specific heat, mean for 0–100 °C (32–212 °F): 813 J/(kg·K) (0.108 Btu/(lb·°F))
• Melting point: 2575 °F, 1413 °C, 1686 K
• Thermal conductivity: 25.5 W/(m·K)
• Mean Coefficient of Thermal Expansion: 11.3×10
-6

• Yield tensile strength: typically 1400-2100 MPa (200,000-300,000 PSI)
• Ultimate strength: typically 1600-2500 MPa (230,000-360,000 PSI). Grades exist up to 3.5 GPa
(500,000 PSI)
• Elongation at break: up to 15%
• K
IC
fracture toughness: up to 175MPam
½

• Young's modulus: 195 GPa
• Shear modulus: 77 GPa
• Bulk modulus: 140 GPa
Variation of Properties:

The dependence of mechanical properties of maraging steels on the temperature of tempering is of the same
pattern as that for all precipitation-hardenable alloys, i.e. the strength properties increase to a maximum, after
which softening takes place. By analogy with ageing, the stages of hardening and softening tempering may be
separated in the process.
The hardening effect is caused by the formation of segregates at dislocations and, what is most important, by the
formation of partially coherent precipitates of intermediate phases of the type Ni
3
Ti or Ni
3
Mo. The softening is
due, in the first place, to replacement of disperse precipitates having greater inter particle spacing and, in the
second place, to the reverse martensitic transformation which is accompanied by the dissolution of intermetallic
in the austenite.
The ultimate strength of maraging steels increases on tempering roughly by 80% and the yield limit, by 140%, i.e.
the relative gain in strength properties is not greater than in typical age-hardening alloys, such as beryllium
bronze or aluminum alloy Grade 1915, but the absolute values of ultimate and yield strength on tempering of
maraging steels reach record figures among all precipitation hardening alloys. This is mainly due to the fact that
maraging steels have a very high strength (R
m
= 1100 MPa) in the initial (as-hardened) state.
The high strength of maraging steels on tempering at 480- 500 ‹C for 1-3 hours may be explained by the
precipitation of very disperse semi coherent particles of the size and inter particle spacing of an order of 10
3
nm
in the strong matrix, these intermetallic precipitates also possessing a high strength. Thus, with the same
disparity of precipitates as that of G. P. zones in precipitation, hardening non-ferrous alloys, maraging steels
possess an appreciably higher ultimate strength (R
m
= 1800-2000 MPa).
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As compared with martensite-hardenable carbon-containing steels, carbonless maraging steels show, for the
same strength, a substantially greater resistance to brittle fracture, which is their most remarkable merit. On
tempering to the maximum strength, the ductility indices and impact toughness, though diminish somewhat, still
remain rather high. The high ductility of the carbonless matrix and the high disparity of uniformly distributed
intermetallic precipitates are responsible for a very high resistance to cracking, which is the most valuable
property of modern high-strength structural materials.
The properties of maraging steels clearly indicate that these steels have many potential applications in
mechanical components of electro-mechanical data processing machines. Use of these steels in shafts that
require good dimensional control following heat treatment should be pursued for two reasons. First, maintaining
dimensions should be easier because quenching and tempering are not necessary. Second, wear data indicate
that equivalent or better wear resistance is obtained from the maraging steel than from the more commonly used
shaft materials.
Impact-fatigue strength of 18% Ni-maraging steels indicates that these steels could be used in repeated impact
loading situations. The good fracture toughness, compared to that of quenched and tempered alloy steels at the
same strength level, indicates possible use in high-impact low-cycle load applications.
Finally, due to the relatively low temperature of aging, the use of the maraging steels for long, thin parts should
be considered. Here, their use as a replacement for some case hardened or nitrided components is indicated
that the potential application should be carefully studied.

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Table 1 summarizes the alloy content of the 18% nickel – cobalt - molybdenum family as developed by Inco in
the late 1950s.
Maraging Steels

% Alloy content
Type
Yield Strength
(0,2% proof stress)
(MPa)
Ni Co Mo Ti Al
18Ni1400 1400 18 8.5 3 0.2 0.1
18Ni1700 1700 18 8 5 0.4 0.1
18Ni1900 1900 18 9 5 0.6 0.1
18Ni2400 2400 17.5 12.5 3.75 1.8 0.15
17Ni1600 (cast) 1600 17 10 4.6 0.3 0.05
Table 1: Summary of the alloy content of the 18% nickel – cobalt - molybdenum family
With yield strength between 1400 and 2400 MPa maraging steels belong to the category of ultra-high-strength
materials. The high strength is combined with excellent toughness properties and weldability.
Typical applications areas include:
• aerospace, e.g. undercarriage parts and wing fittings,
• tooling & machinery , e.g. extrusion press rams and mandrels in tube production, gears
• Ordnance components and fasteners.
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Maraging 250

Maraging 250 is an 18 percent nickel steel that has been strengthened with cobalt. Maraging 250, like all
maraging steels, goes through an aging process that forces the metal to cool from its molten state to its
solid state over an artificially long time. This process results in a tempered steel that has both high levels of
strength and hardness. It will also resist certain stresses and maintain its structure in environments that
would cause irreparable changes to many other steels.
The properties that make Maraging 250 particularly appealing to many industries is its workability. This
allows Maraging 250 to be more versatile than many other alloys in its class. However, it is still the alloy's
strength and resistance to extreme temperatures that make it a truly effective material in a wide range of
atmospheres. After Maraging 250 has undergone heat treatment, it demonstrates excellent mechanical
properties. It will reach a yield strength of 240 ksi and a fracture toughness of 75 kic. These properties have
made Maraging 250 effective in the construction of missile and rocket motor cases, landing and takeoff gear,
and high-performance shafting.
Alloy Steels Maraging 250
Related Metals: VascoMax 250(tm)
Specifications: DIN 1.6358
Chemistry Data
Aluminum
Boron
Carbon 0.03 max
Cobalt
Iron Balance
Manganese 0.1 max
Molybdenum
Nickel
Phosphorus 0.01 max
Silicon 0.1 max
Sulphur 0.01 max
Titanium
Zirconium
Physical Data
Density (lb / cu. in.) 0.289
Maraging Alloy 250 - Age Hardenable (Maraging) Iron-Nickel Steel from Super Alloys
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Maraging 300

Maraging 300 is an iron-nickel steel alloy that, as with all maraging steels, exhibits high levels of strength
and hardness. However, Maraging 300 also possesses an extreme resistance to crack propagation, even in
the most extreme environments. Maraging 300 is often used in applications where high fracture toughness
is required or where dimensional changes have to remain at a minimal level.
The unique properties of Maraging 300 have made it a integral part of the aircraft and aerospace industries.
It is often used in rocket motor casings and the landing gear for certain planes. Maraging 300 is also
effective in the design of power shafts and low-temperature cooling systems.
Alloy Steels Maraging 300
Specifications
The following specifications cover Alloy Steels Maraging 300: DIN 1.6354
Property Results Related Metals: VascoMax 300 (tm)
Chemistry Data
Carbon : 0.03 max
Iron : Balance
Manganese : 0.1 max
Phosphorus : 0.01 max
Silicon : 0.1 max
Sulphur : 0.01 max

Principal Design Features
Maraging 300 alloy is a very high strength iron base, nickel , molybdenum, cobalt alloy. It may be age hardened to a strength
level of 300 ksi ultimate with a hardness on the order of Rockwell C 53.

Applications
Used for very high strength structural applications such as aircraft land gear components.
Machinability
Machinability is good, similar to that for 304 stainless steel.
Forming
Maraging 300 steel has good ductility and is readily formed by conventional methods.
Welding
The alloy is weldable by conventional methods, much the same as for 304 stainless steel.
Heat Treatment
Maraging steel is not heat treatable for hardening except by aging. See "Aging".
Forging
The alloy may be forged as for stainless 304 alloy.
Hot Working
Hot working of maraging steel may be done at temperatures in the 500 to 200 F range. Prolonged exposure at these
temperatures may result in some age hardening. However a full aging treatment should be given.
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Cold Working
The alloy is readily cold worked by conventional methods.
Annealing
Annealing, if required after cold working, can be done at 1900 F followed by rapid air cooling.
Aging
The high strength and hardness properties are a result of an aging heat treatment at 900 F
Tempering
Not applicable to this alloy.
Hardening
Maraging 300 hardens by cold working and by aging - see "Aging".

Physical Data
Density (lb / cu. in.) 0.289
Specific Gravity 8
Specific Heat (Btu/lb/Deg F - [32-212 Deg F]) 0.108
Melting Point (Deg F) 2575
Thermal Conductivity 136
Mean Coeff Thermal Expansion 5.6
Modulus of Elasticity Tension 27.5

More technical information:
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Maraging 350

Maraging refers to a crystalline tempered steel, Martensite, that is created through an aging process. When
aging is used, steel is forced to cool from its molten state to its solid state over a prolonged period of time.
The result is a metal that is harder and stronger than it would be had the steel been allowed to cool at a
natural rate.
Maraging 350 is an alloy that has become an integral material in the airplane and aerospace industries.
Due to its strength and its ability to withstand extreme conditions including frequent and sudden changes in
speed and temperature, Maraging 350 is used in the production of rocket motor cases, takeoff and landing
gear, and certain munitions created by defense companies. Maraging 350 also has uses in less drastic
applications such as die casting and high-performance shafting.
Maraging 362

Maraging materials are known for their exceptional strength and hardness. Their ability to resist various
forms of stress in extreme environments has made maraging steels commonplace in the aerospace and
aircraft industries. Each maraging alloy has its own unique qualities, but many of them are used in similar
applications.
Maraging 362, like other maraging steels, undergoes an artificial aging process. This process leads to the
material's added strength and hardness. The results of the aging procedure has recently caught the eye of
golf club designers and manufacturers who have begun to use maraging alloys on the faces of their clubs in
the hope that players will see increased power and that clubs will not corrode over time.
Maraging Steel

Maraging steel gives you an elevated level of strength, hardness, and ductility. These steels are created
through an aging process that results in the development of a hard, brittle crystalline called martensite. The
term "maraging" is, in fact, a simple combination of martensite and aging.
The construction of maraging steel allows it to withstand atmospheres that would quite simply destroy most
standard steel. The aging process instills maraging steel with the ability to withstand sudden changes in
speed and temperature, even at extreme levels. This quality has made maraging steel alloys an important
component of many of the air and spacecraft used today.
Its specific use in military programs and space programs has made maraging steel a rather unique material.
It is not generally carried by small-scale metals companies. Instead, it can be found through distributors
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who regularly work with organizations in the aerospace and aeronautical industries. A metals company that
has the capacity to supply maraging steel will usually distribute a wide range of hard-to-find alloys.
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The Periodic Table:

The Atomic Radii:



In specifying values for the radius of an atom, one must keep in mind the fact that atoms are not hard spheres,
and the electron distribution in the outer part of the atom does not have a sharp cutoff radius. You could
characterize the radius of the atom as a limiting radius where a certain percentage of the electron charge will be
found. The illustration above is a plot of "covalent radii" (from Ebbing) which are determined by measuring the
bond lengths in the molecules of chemical compounds. Another way to determine characteristic radii is to
measure ionic radii in crystals using x-ray diffraction. If the crystalline composition is such that the ions can be
considered to be in contact with each other, and you can determine the lattice spacing from x-ray diffraction, then
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Page 169 of 180
you can imply the ionic radius. As might be expected, the ionic radius of negative ions is slightly larger than the
covalent radius since they have extra electronic charge, and that of positive ions is slightly smaller.

Atoms and Nuclei
http://www.practicalphysics.org/go/Topic_40.html?topic_id=40


Schaeffler diagram.
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Page 170 of 180
Precipitation hardening stainless steels

Precipitation hardening stainless steels like the martensitic types, can be strengthened by heat treatment.
The mechanism is metallurgically different to the process in the martensitic types. This means that either
martensitic or austenitic precipitation hardening structures can be produced. This family of stainless alloys
utilizes a thermal treatment to intentionally precipitate phases, which cause a strengthening of the alloy. The
principle of precipitation hardening is that a supercooled solid solution changes its metallurgical structure on
aging. The advantage is that products can be fabricated in the annealed condition and then strengthened by
a relatively low temperature treatment, minimizing the problems associated with high temperature treatment.
Precipitation hardening stainless steel has high strength and relatively good ductility and corrosion
resistance at high temperature. They reach these high strengths by precipitation of intermetallic compounds
Alloy 17-4PH

Sandmeyer Steel Company stocks a large inventory of 17-4PH stainless steel plate in the annealed
condition in thicknesses from 3/16" through 3", ready to be processed and shipped to your specific
requirements.
Alloy 17-4PH is a precipitation hardening martensitic stainless steel with Cu and Nb/Cb additions. The grade
combines high strength, hardness (up to 572°F /300°C), and corrosion resistance. Mechanical properties
can be optimized with heat treatment. Very high yield strength up to 1100-1300 MPa (160-190 ksi) can be
achieved.
17-4PH (UNS S17400)
A 17Cr-4Ni-3Cu Precipitation Hardening Martensitic Stainless Steel

General Properties
Applications
Standards
Corrosion Resistance
Chemical Analysis
Mechanical Properties
Physical Properties
Heat Treatment
Processing
Welding
Machining

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Page 171 of 180
General Properties

Alloy 17-4 PH is a precipitation hardening martensitic stainless steel with Cu and Nb/Cb additions. The grade
combines high strength, hardness (up to 572°F / 300°C), and corrosion resistance.
Mechanical properties can be optimized with heat treatment. Very high yield strength up to 1100-1300 MPa
(160-190 ksi) can be achieved.
The grade should not be used at temperatures above 572°F (300°C) or at very low temperatures. It has
adequate resistance to atmospheric corrosion or in diluted acids or salts where its corrosion resistance is
equivalent to Alloy 304 or 430.
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Applications
• Offshore (foils, helicopter deck platforms, etc.)
• Food industry
• Pulp and paper industry
• Aerospace (turbine blades, etc.)
• Mechanical components
• Nuclear waste casks
Back to top

Standards
ASTM.....................A693 grade 630 (AMS 5604B) UNS S17400
EURONORM...........1.4542 X5CrNiCuNb 16-4
AFNOR...................Z5 CNU 17-4PH
DIN.........................1.4542
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Corrosion Resistance
Alloy 17-4 PH withstands corrosive attacks better than any of the standard hardenable stainless steels and is
comparable to Alloy 304 in most media.
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Page 172 of 180
If there are potential risks of stress corrosion cracking, the higher aging temperatures then must be selected
over 1022°F (550°C), preferably 1094°F (590°C). 1022°F (550°C) is the optimum tempering temperature in
chloride media.
1094°F (590°C) is the optimum tempering temperature in H2S media.
The alloy is subject to crevice or pitting attack if exposed to stagnant seawater for any length of time.
It is corrosion resistant in some chemical, petroleum, paper, dairy and food processing industries (equivalent
to 304L grade).
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Chemical Analysis
Typical values (Weight %)
C Cr Ni Cu Nb/Cb Mn
0.04 16.5 4.5 3.3 0.3 0.7
PREN (%Cr+3.3%Mo+16%N) ≥17
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Mechanical Properties
Room temperature properties (longitudinal direction)
Guaranteed values (ASTM A693 hot rolled plates); thickness from 3/16" up to 3".
YS 0.2%
N/mm
UTS
N/mm
YS 0.2%
ksi
UTS
ksi
El%
Heat
treatment
Min. Typ. Min. Typ. Min. Typ. Min. Typ. Min. Typ.
A 1070 1207 1170 1310 155 175 170 190 8 14
B 790 931 965 1034 115 135 140 150 10 17
A: hardening 925°F (496°C) - 4 hours - air cooling
B: hardening 1100°F (593°C) - 4 hours - air cooling
2 examples of heat treatments that may be applied.
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Elevated temperature properties
Minimum guaranteed values following EN 10088 hot rolled plates. The EN guaranteed values are valid for a
thickness from 3/16" up to 3".
Temperature °F
Temperature °C
212
100
302
150
392
200
482
250
572
300
N/mm_ 730 710 690 670 650
YS
0.2%
ksi 106 103 100 97 95
Heat treatment : hardening 1094°F (590°C) - 4 hours - air cooling. 1 example of heat treatments that may be
applied.
Minimum guaranteed room temperature impact values
Minimum guaranteed values following ASTM A693 hot rolled plates. The ASTM guaranteed values are valid
for a thickness from 3/16" up to 3".
KV transverse
Heat treatment
J ft.lbf
Hardening 1100°F (593°C) - 4
hours - air cooling
20 15
Minimum guaranteed room temperature hardness values
Minimum guaranteed values following ASTM A693 hot rolled plates. The ASTM guaranteed values are valid
for a thickness from 3/16" up to 3".
Hardness
Heat treatment
Rockwell Brinell
Hardening 925°F (496°C) - 4
hours - air cooling
C38 375
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Physical Properties
Density: 7800 kg/m3 (.28 lbs/in3)
Following physical properties have been obtained after hardening 896°F (480°C) – 1 hour - air cooling.
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Interval
Temperature
°C
Thermal
expansion
x10
-6
°C
-1

°C °F
Thermal
conductivity
(w.m
-1
.K
-1
)
Young
modulus
(GPa)
0-100 10.8 20 68 14 197
0-200 11 100 212 16 193
0-300 11.3 200 392 18.5 186
0-400 11.6 300 572 20 180
0-500 12 400 752 22 175
500 932 23 170
Room temperature properties:
Resistivity : 80 µ*.cm
Specific heat : 460 J.kg
-1
.K
-1

Tension modulus : 77 GPa
The alloy is magnetic.
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Heat Treatment
Martensitic transformation
Indicative values
Ms : 266°F (130°C)
Mf : 86°F (30°C)
Solution annealing
1925°F+ /-50°F (1050°C +/-25°C) – 30 min up to 1 hour.
air cooling / oil quenching below 76°F (25°C)
Aging / Tempering
The highest mechanical properties are obtained with the following heat treatment : 896°F (480°C) – 1 hour –
air cooling. Higher ductilities are obtained when using higher aging temperatures up to 1148°F (620°C).
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Page 175 of 180

Hardness/Temperature tempered for 4 hours after austenitizing at 1904°F (1040°C) for 30 min quenched
212°F/sec (100°C/sec).
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Processing
Hot Forming
Hot forming should be carried out in a temperature range of 1742-2192°F (950-1200°C). A full heat
treatment including solution annealing, cooling lower than 76°F (25°C) and aging at the required temperature
must be made after hot forming (function of the requested mechanical properties).
Cold Forming
Cold forming can be performed only to a limited extent and only on plates in the fully softened condition.
Stress corrosion resistance is improved by re-aging at the precipitation hardening temperature after cold
working.
The following processes may be performed: rolling, bending, hydroforming, etc. (fully softened conditions).
Cutting
Thermal cutting (plasma, thermal sawing, etc.). Due to the HAZ, the grade requires a suited cutting process.
After cutting, grinding is necessary to eliminate the oxide formed layer.
Mechanical cutting (shearing, stamping, cold sawing, etc).
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Welding
Alloy 17-4 PH can be welded by the following welding processes: SMAW, GTAW, PAW and GMAW. SAW
should not be used without preliminary testing (to check freedom of cracks and toughness of the weld metal).
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Page 176 of 180
Due to a ferrite delta primary type of solidification, the hot cracking risk of the weld metal or the HAZ is
reduced.
Generally, no preheating must be done and interpass temperature must be limited to 248°F (120°C). The
better toughness is obtained in the weld after a complete heat treatment (solution annealing + precipitation
hardening).
Due to the martensitic microstructure, a low oxygen content in the weld metal is preferable to increase
ductility and toughness. To avoid cold cracking, the introduction of hydrogen in the weld must be limited.
Alloy 17-4 PH can be welded with homogeneous filler metals such as E 630 (AWS A5.4) electrodes and ER
630 (AWS A5.9) wires.
Austenitic filler material can be used when the mechanical properties of 17-4 PH steel are not required in the
weld and, in this case, no post-weld heat treatment must be applied.
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Machining
Alloy 17-4 PH can be machined in both solution treated and precipitation hardened conditions. Machining
condition may vary according to the hardness of the material. High speed steel tools or preferably carbide tools
with standard lubrification are normally used. If very stringent tolerances are required, it is necessary to take into
account the dimensional changes during heat treatment.




















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Page 177 of 180
Thermal Processing of Metal:


http://www.tntech.edu/me/courses/Zhang/ME30103110/Chap11pt3.ppt



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Page 178 of 180







Online reading materials:

Ductile Iron Tutorial
http://www.ductile.org/didata/Section2/2intro.htm
Alloys and Stainless Steels
http://www.roymech.co.uk/Useful_Tables/Matter/Alloy_Steels.html
Metallurgical Engineering
http://www.sut.ac.th/Engineering/Metal/course.html
Matters
http://www.matter.org.uk/steelmatter/metallurgy/default.htm
Microplasticity: dislocations and strengthening mechanisms
http://www-sgrgroup.materials.ox.ac.uk/lectures/microplasticity.html
Steel Heat Treatment: Metallurgy and Technologies
http://www.ebookee.com.cn/Steel-Heat-Treatment-Metallurgy-and-Technologies_148046.html
Metallurgy fundamentals.
http://rapidshare.com/files/9027049/Metallurgy_Fundamentals_Warner_Brandt.djvu.html
Solid-State Phase Transformations in Steels
http://upload.sms.csx.cam.ac.uk/collection/19

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Page 179 of 180
Stainless Steel Data.
http://www.sandmeyersteel.com/precipitation-hardening.html
Stainless Steel grades data.
http://www.bssa.org.uk/topics.php?article=59
Materials and Processes in Manufacturing
http://www.tntech.edu/me/courses/Zhang/ME30103110/
Engineering Materials and physical metallurgy.
http://www.sut.ac.th/Engineering/Metal/course.html






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DEFORMATION-MECHANISM MAPS The Plasticity and Creep of Metals and Ceramics
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Page 180 of 180





Additional Reading

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Appendix A.
More reading:

http://www.sut.ac.th/Engineering/Metal/course.html

Applied Metallurgy
http://www.esdep.org/members/master/wg02/toc.htm
Steels
http://www.key-to-steel.com/default.aspx?ID=Articles&LN=EN
Material Property Search
http://www.matweb.com/search/QuickText.aspx?SearchText=4140

http://www.matter.org.uk/default.htm
The Alloying Elements in Steel, by Edgar C. Bain
http://www.msm.cam.ac.uk/phase-trans/2004/Bain.Alloying/ecbain.html
Material Science Course
http://info.lu.farmingdale.edu/depts/met/met205/index.html

http://www.cs.slcc.edu/engr/moore/mse/mse2010.html
Now you can perform virtual tensile testing.
http://www.uow.edu.au/cedir/progservs/samples/anim_ENGG153/intro.swf


Articles on steel making and inclusions:
Steel making: http://www.sigi.ca/engineering/documents/steel_making.pdf
Effects of deoxidation practice on the inclusion formation:
http://www.ferroforsk.com/ekstern/publications/mikron/PaperStockholm2000.pdf
Slag inclusion formation during solidification:
http://www.diva-portal.org/diva/getDocument?urn_nbn_se_kth_diva-4371-2__fulltext.pdf
Introduction to materials and processes:
http://www.ndt-ed.org/EducationResources/CommunityCollege/Materials/cc_mat_index.htm



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Appendix A.

Chapter1: http://www.cs.slcc.edu/engr/moore/mse/lectures/chapter1_files/frame.htm
All Chapters: http://www.cs.slcc.edu/engr/moore/mse/lectures/

http://mc-mjnde.ornl.gov/Babu/Teaching/Brazil/PTFolder/SolidFol/sld001.htm


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Appendix A.


Ahindra Ghosh, "Secondary Steelmaking: Principles and Applications"
CRC; 1 edition (December 13, 2000) | ISBN: 0849302641 | 344 pages | PDF | 17 Mb

well as modify harmful nonmetallic inclusions and achieve the optimum casting temperature,
content of alloying elements, and homogeneity. These improvements can come only through
the diverse refinement processes that together comprise "secondary steelmaking."
Secondary Steelmaking: Principles and Applications reviews the scientific fundamentals and
explores the various unit processes associated with secondary steelmaking. Synthesizing the science and its
technology, the author examines the relevant reactions and phenomena, presents an integrated picture of "clean
steel" manufacture, and provides an overview of the mathematical modeling important to process research.
Solved examples, ample references, and summaries of recent technological advances mean that the
steelmaking industry finally has a comprehensive reference, in English, for the all-important secondary
steelmaking processes. Students and instructors, steelmakers and R & D engineers will welcome the author's
readable style, his knowledge, and his expertise, all gleaned from decades of experience in research, academic,
and industrial settings.
http://depositfiles.com/files/2287630
MIRROR : http://www.icefile.net/index.php?page=main&id=e95461423&name=Steelmaking.7z


A wealth of data on metals and their extraction is revealed in this
comprehensive handbook. The aim of this book is to provide a clear
description of how a particular metal is extracted industrially from different
raw materials, and on what its important compounds are. The present
work is a collection of 58 articles written by over 280 specialists. It supplies
thousands of top-quality illustrations, diagrams and charts, and provides
hand-picked references ensuring the most up-to-date coverage. A unique
feature of this reference work is its structure. The system used here is
according to an economic classification, which reflects mainly the uses,
occurrence and economic value of metals. First, the ferrous metals, i.e.,
those used in the production of iron and steel, are outlined. Then,
nonferrous metals are subdivided into primary, secondary, light, precious,
refractory, scattered, radioactive, rare earth, ferroalloy metals, and, finally,
the alkali and the alkaline earth metals are described.
The handbook is an essential aid for the practising metallurgist. Mining
engineers, mineralogists, chemical engineers, chemists and geologists will find it a comprehensive desk
reference. It is of interest to engineers and scientists in industry seeking an exhaustive sourcebook, and it should
be present in every library.

http://rapidshare.com/files/13898521/20062007.part1.rar
http://rapidshare.com/files/13945593/20062007.part2.rar

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Appendix A.

Steel Heat Treatment: Metallurgy and Technologies
(Steel Heat Treatment Handbook)
CRC | 848 pages | 2006-09-28 | ISBN: 0849384559 | PDF | 33.3MB

One of two self-contained volumes belonging to the newly revised Steel
Heat Treatment Handbook, Second Edition, this book examines the
behavior and processes involved in modern steel heat treatment
applications. Steel Heat Treatment: Metallurgy and Technologies
presents the principles that form the basis of heat treatment processes
while incorporating detailed descriptions of advances emerging since
the 1997 publication of the first edition. Revised, updated, and
expanded, this book ensures up-to-date and thorough discussions of
how specific heat treatment processes and different alloy elements
affect the structure and the classification and mechanisms of steel
transformation, distortion of properties of steel alloys. The book includes
entirely new chapters on heat-treated components, and the treatment of
tool steels, stainless steels, and powder metallurgy steel components. Steel Heat Treatment: Metallurgy and
Technologies provides a focused resource for everyday use by advanced students and practitioners in
metallurgy, process design, heat treatment, and mechanical and materials engineering.
http://rapidshare.com/files/59830510/Steel_Heat_Treatment_0849384559.rar

Madeleine Durand-Charre , «Microstructure of Steels and Cast
Irons»
Publisher: Springer | Number Of Pages: 404 | Publication Date: 2004-04-15 |
ISBN / ASIN: 3540209638 | PDF | 24 MB

The book comprises three parts. Part 1 gives a historical description of the
development of ironworking techniques since the earliest times. Part 2 is the
core of the book and deals with the metallurgical basis of microstructures, with
four main themes: phase diagrams, solidification processes, diffusion, and solid
state phase transformations. Part 3 begins by an introduction to steel design
principles. It then goes on to consider the different categories of steels, placing
emphasis on their specific microstructural features. Finally, a comprehensive
reference list includes several hundred pertinent articles and books. The book is
the work of a single author, thus ensuring uniformity and concision. It is
intended for scientists, metallurgical engineers and senior technicians in research and development laboratories,
design offices and quality departments, as well as for teachers and students in universities, technical colleges
and other higher education establishments.
http://rapidshare.com/files/44188131/Microstructure.of.Steels.and.Cast.Irons_muya.rar



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Appendix A.



Metallurgy Fundamentals
By Daniel A. Brandt,&nbspJ. C. Warner,
* Publisher: Goodheart-Wilcox Publisher
* Number Of Pages: 301
* Publication Date: 2004-02
* ISBN / ASIN: 1590703456
An excellent introduction to metal making
I found Metallurgy Fundamentals to be an
excellent resource for myself. While not
overly technical it covers the basic principles
and theory of metal making in clear and
straightforward language. I recommend it for
persons in drafting, quality, design, or
purchasing
114 MB ~ Pdf. Good Quality.









Part 1 http://rapidshare.com/files/37614440/Metallurgy_Fundamentals__Brand_Warnr.part1.rar
Part 2 http://rapidshare.com/files/37622602/Metallurgy_Fundamentals__Brand_Warnr.part2.rar
--------------
http://rapidshare.com/files/37614440...arnr.part1.rar
http://rapidshare.com/files/37622602...arnr.part2.rar




_
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http://www.alhandasa.net/forum/showthread.php?t=141104
http://www.alhandasa.net/forum/showthread.php?p=1549563
Scanned copy-poor quality, however it is simple,
informative, lots of photos and educational




Slag inclusion formation during solidification of Steel
alloys and in cast iron


Sofia Adolfi



Licentiate Thesis

Materials Processing
Department of Material Science and Engineering
School of Industrial Engineering and Management
Royal Institute of Technology
SE-10044 Stockholm, Sweden
Akademisk avhandling som med tillstånd av Kungliga Tekniska Högskolan i Stockholm framlägges till offentlig
granskning för avläggande av teknologie Licentiatexamen, fredagen den 11 maj 2007, kl. 10:00, Sal B1, Brinellvägen 23,
KTH, Stockholm.
ISSNKTH/MSE-07/10-SE+CER/AVH, ISBN 978-91-7178-624-1


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Sofia Adolfi, Slag inclusion formation during solidification of Steel alloys and in
cast iron





School of Industrial Engineering and Management
Department of Materials Science and Technology, Materials Processing
Royal Institute of Technology
SE-100 44 Stockholm, Sweden

ISSN KTH/MSE-07/10-SE+CER/AVH
ISBN 978-91-7178-624-1
© Sofia Adolfi March 2007

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Slag inclusion formation during Solidification of Steel alloys and in cast iron
Sofia Adolfi 2007
Department of Materials Science, Royal Institute of Technology
S-100 44 Stockholm, Sweden
Abst ract
This thesis explores the formation of segregation and inclusions during solidification
of steel and cast iron. A better understanding of the formation mechanism should result
in decreasing fraction of defects during solidification of ingot and strand material.
Density driven macrosegregation was studied both experimentally and theoretically to
see the effect of channel segregation on the total segregation. Formation of these pencil-
like segregations is due to natural convection in the solidifying metal caused by liquid
enrichment of elements with lower density compared to the bulk. It is suggested to
change the composition to compensate for this density difference.
Inclusion precipitation can be finite by limitations in segregation. Saturated liquid is
found in the last solidified areas, often between dendrites. Here the enrichment of the
liquid is possible due to microsegregation. Meanwhile crystals form and solidify the
elements with low solubility in the solid is pushed out in the remaining liquid. Soon the
liquid is saturated to the level where spontaneous formation of inclusions occurs.
Microstructure studies by aid of SEM and micro-probe measurements are analysed to
find at what point during solidification process the inclusions start to form. In steel
making this formation has a detrimental effect on the mechanical properties in contrary
to the production of nodular cast iron where the inclusions have a beneficial effect on
the graphite formation.
Inoculation of cast iron aims at reaching higher number density of graphite nodules,
nodule morphology modification and control of nodule distribution during solidification.
Late precipitation of nucleation sites has shown to have a positive impact on preventing
chill. To find the most potent inoculation agent different additives were tested. Special
effort has been made to analyse the effect of oxides and sulphides as nucleation sites.
Descriptors: solidification, segregation, precipitation, inclusions, inoculation, EPMA
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Supplement s
The thesis includes the following supplements

Supplement 1
Crack formation during continuous casting of tool steel
A. Lagerstedt, S. Adolfi and H. Fredriksson
Trans. Indian Inst. Met. Vol. 58, No. 4, August 2005, pp. 671 – 678
I performed the hot-tensile tests, evaluation and part of report writing

Supplement 2
Macrosegregation in ingot cast tool steel
A. Lagerstedt, J. Sarnet, S. Adolfi and H. Fredriksson
ISRN KTH-MG-INR-04:09 SE
TRITA-MG 2004:09
I took part in all experiments and part of final evaluation and report writing. In particular
I performed the temperature measurements and EPMA analysis

Supplement 3
A thermodynamic analysis of the inoculation process
L. Magnusson, S. Adolfi and H. Fredriksson
ISRN KTH-MG-INR-06:03 SE
TRITA-MG 2006:03
I performed the experimental part and together with Lena Magnusson the theoretical
evaluation

Supplement 4
MnS precipitation during solidification in presence of oxide nuclei
S. Adolfi, K. Mori and H. Fredriksson
Accepted to the 5
th
Decennial International Conference on Solidification Processing
I performed the experiments and report writing
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Cont ent s
1. I nt roduct ion 1

2. Experiment al met hods 3
2. 1 Mat erial pr eparat ion 3
2. 2 Thermal propert ies 3
2. 2. 1Different ial Thermal Analysis 3
2. 2. 2 “ I n- sit u” solidified hot t ensile t est s 4
2. 3 Macrosegregat ion st udy 5
2. 4 I nclusion st udy 6
2. 4. 1 I nclusion char act erist ics 6
2. 4. 2 Elect ron Probe Micro- Analysis 6
2. 5 I noculat ion in nodular cast iron 7
3. Result s 8
3. 1 Macrosegregat ion 10
3. 2 I nclusion char act erist ics 10
3. 3 I noculat ion in nodular cast iron 10
4. Discussion 13
5. Conclusions 15
6. Fut ure work 17
7. References 21

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1
1 I nt roduct ion
The aim of this study was to analyse the solidification process in steel alloys and cast
iron. Focus has been on segregation and defects and their formation mechanism. Both
experimental and theoretical method to analyse this has been used. A great part of the
work has been to design the proper experiment. The experimental outcomes are used for
further theoretical work.
During solidification of steel ingots and strand compositional variations referred to as
macrosegregation range in scale from several millimetres to centimetres or even metres.
The in-homogenous distribution of alloy elements have a detrimental impact on the
following processing behaviour and the material properties and can lead to rejection of
cast components or processed products. The formation of these variations is driven by
natural convection where hot metal will flow upward inside the centre of the ingot and
cooler solidifying liquid will grow heavier in density and flow downward the mould wall.
At this stage some crystal with lower liquidus temperature can remelt while in contact
with the high-temperature melt leading to channel formation where highly segregated
liquid will flow upwards due to its lower density. During solidification crystals will freeze
at the solidus temperature and gradually form a solid. This solid will continue to grow
meanwhile the remaining liquid will be enriched by elements with lower solubility in solid
phase compared to the liquid. This enrichment or commonly referred to as
microsegregation will open up for precipitation of other phases, inclusions which benefit
from the saturation of alloying elements.
Hot cracks are often the result from the solidification process. The material will go
through a brittle to ductile transformation during solidification. The brittle region causes
this crack formation. This brittleness is caused by the presence of thin liquid films in the
interdendritic region at the crystal boundaries.
1
These are often type II MnS inclusions.
By means of hot-tensile-tests, DTA and Electron Probe Micro-analysis the proper
material data can be found for further theoretical analysis on crack- and inclusion
formation. Inclusions in steel are categorized according to type (chemical composition)
and morphology (shape). They origin either from before casting or they spontaneously
precipitate during solidification. The first case is often a result from secondary metallurgy
and can be an effect of slag or mould material being dragged into the liquid steel. This
type is often referred to as macro slag. Precipitation of inclusion during solidification is
possible when the supersaturation needed to form a certain compound is reached in the
liquid and the formation facilitates by presence of small nuclei, mainly of oxide type. One
of the most common inclusions is the MnS. Early it was discovered by Sims and Dahle,
2

they are of different morphology due to formation process. They classified the globular
shaped as type I, enveloped thin sheeted as type II and the faceted ones as type III. Later
work made by Fredriksson and Hillert,
3
revise this classification by adding the type IV
morphology, a lamellar eutectic structured MnS. They suggest that the formation of
types I and II are by a monotectic reaction where MnS forms as a liquid phase. Types III
and IV are a eutectic reaction where MnS forms a crystalline phase. A monotectic
reaction is a process in which a melt gives a solid phase and another liquid phase,
L1→α+L2. A eutectic reaction is a solidification process in which a liquid solidifies to
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2
two solid phases, L→α+β. The type of MnS inclusion depends on many variables. The
main factors are: cooling rate, concentrations of Mn and S in the melt, the solubilities of
the alloying elements in molten MnS + Fe and the deoxidation process of the melt.
Common deoxidants are Al and Si. Another method to reduce O concentration is
vacuum degassing.
During solidification inclusions are pushed in front, entrapped or engulfed by the
solidifying front. Stefanescu et al.,
4
explain there exist a critical velocity of the planar
solid – liquid interface below which particles are pushed ahead of the advancing front
and above which particle engulfment occurs. Engulfment is used to describe
incorporation of a particle (i.e. inclusion) by a planar interface and entrapment is used to
explain how particles incorporate between cells and dendrites. Engulfment will normally
lead to a uniform particle distribution, while pushing will result in particle segregation.
Later studies by Stefanescu et al.
5
show that particle interaction with dendritic solid –
liquid fronts can be explained with similar controlling parameters as for planar fronts.
Based on dendrite tip radius, particle radius, natural convection induced liquid velocity,
VL, and the solidification velocity, VSL, engulfment or entrapment occurs. Engulfment
can occur if convection is low and surface velocity is high. Slow interface velocity result
in particle being entrapped between dendrite arms. However if VL is high but VSL is
small the particle will be pushed in front of the interface. These types of defects in steel
production should be possible to decrease by better understanding on the formation
mechanism.
Precipitation of oxides and sulphides has a beneficial effect on the graphite formation
in production of nodular cast iron. The inclusions act as nucleation sites for graphite. By
addition of different inoculation agents we can promote nodularity, refine the graphite
structure and suppress carbide formation. In earlier work by Skaland,
6
it is suggested that
different oxides and sulphides may increase the inoculation effect. Oxide and sulphide
inclusions which are formed after addition of the inoculants act as nucleation sites for
graphite nodules. To find the most potent inoculants we studied the nucleation process
of graphite in presence of different inoculation agents. In contrary to inclusions formed
during steel making precipitation of oxides and sulphides is most wanted.
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3
2 Experiment al met hods
2. 1 Mat erial preparat ion
The material used in this thesis work is presented in table 1, supplement 4. Steel A is
represented by one octagonal 12 ton ingot and one rectangular 10 ton ingot produced by
uphill casting at Scana Steel Björneborg AB. Steel B comes from a continuous casting
experiment carried out in slab caster 2 at SSAB Oxelösund AB. Steel C is a aluminium-
killed 6 ton ingot produced by uphill casting at Ovako AB. Ingots were cold sawed to
pieces in order to allow for sulphur printing and drilling for chemical composition to
obtain the segregation pattern of C and S. The old but well known Sulphur printing
technique was re-discovered and prints were made on sawed surfaces in order to obtain
macrographs of the ingot structure. To get as detailed information as possible from the
prints some surfaces was milled to give good sharpness. Photo paper was soaked in 5%
sulphuric acid and rolled on to the metal surface in good contact. The prints are taken at
the vertical cross section. Sample drilling was performed over the vertical cross section
to obtain the segregation pattern of C and S.
Test with different inoculation additives are made on a base alloy of white nodular
vast iron, presented in table 1, supplement 3.
2. 2 Thermal propert ies
2. 2. 1 Different ial Thermal Analysis
Differential Thermal Analysis, DTA was used to study the solidification process. The
result is used as in-data for further theoretical calculations. During heating and cooling
the sample temperature was measured and any transformation will be shown as a change
in temperature compared to a known reference state. The technique is to measure the
difference in temperature between the specimen and a known reference which are
exposed to the same heating schedule. The reference could be any material with about
the same thermal mass as the sample, which undergoes no transformations in the
temperature range of interest. When the sample undergoes a transformation it will either
absorb or release heat. The thermocouple will detect and indicate if the transformation is
“exothermic” on a plot of temperature versus time. Heating rate is an important
consideration in this investigation. Slower heating rate will more accurately depict the
onset temperature of a transformation. Furthermore two transformations which are very
close in temperature range may be mistaken for a single transformation under rapid
heating rate. Measurements were performed using a resistant heated tube furnace. A
graphite cylinder was place around the alumina crucible both to be used as reference but
also to prevent convection in the melt. A constant heating and cooling rate of 10°C/min
was used. Argon is used as shield gas. Temperature was measured by PtRh10%-Pt
thermocouples. Calibration was performed with pure silver resulting in corrections of
about +3°C and the measuring device work with an accuracy of ± 1°C. Sample
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4
dimension was 7 mm in diameter, 14 mm in height with a 3 mm wide and 9 mm deep
centre hole drilled to fit the thermocouple. Data were sampled 20 times every second.

5000 5200 5400 5600 5800 6000 6200 6400 6600 6800 7000
1300
1350
1400
1450
1500
Time [s]
T
e
m
p
e
r
a
t
u
r
e

[
°
C
]
exothermal process
reference
sample

Figure 1: Temperature vs. time curve (DTA)
2. 2. 2 “ I n- sit u” solidified hot t ensile t est s
The high temperature parameter known as the transition temperature from ductile- to
brittle fracture, TDB can be used as indicator if a metal is crack sensitive. In the study on
crack formation during solidification of liquid metal this is a technique to find proper
material data for further mathematical modelling. This temperature is measured during
solidification and cooling of the metal and correspond to the point when the metal start
to have a brittle mechanical behaviour. At temperatures below the transition we find
plastic behaviour with necking and ability to high elongation and strains leading to
ductile fractures. Low transition temperatures, below the metal solidus temperature
indicate crack sensitivity.
This specific temperature can be measured by high temperature tensile testing of in-
situ solidified samples. The technique is from the beginning used in the work of Rogberg
and Fredriksson, and additionally developed by Karin Hansson.
7
The concept is to have
a mirror furnace, which can be inserted into a tensile testing machine. The mirror
furnace gives a limited heating zone by its focus, which makes it possible to melt a small
part of the sample and let it solidify and cool to the tensile test temperature. This
technique has the advantage that one can melt the sample and let it solidify with a
controlled cooling rate which can simulate the real conditions in the casting process with
regards to cooling rate, microsegregation etc.. The mirror furnace consists of three gold
plated ellipsoidal reflectors with a halogen lamp inserted at the focal point. Using a
maximum power of 1020 W and the centre of the test specimen placed in focal point a
5mm long melting zone was formed and held in place by the surface tension. The
temperature was measured with thermocouples of type S made of Pt-Pt10%Rh placed in
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5
the centre of the melting zone. A quartz tube with argon atmosphere is placed around
the specimen to protect it from oxidation. The reflectors and tensile rods were water-
cooled. Elongation is measured by an extensometer. Force is measured with a load cell
of 5kN in a range of ± 2.5kN. Force, position of the piston, elongation and temperature
is sampled by the computer controlling the tensile test machine. Tensile specimens of 40
mm length and 4 mm diameter were heated up to TL+5° and then cooled down with a
constant rate of 2°C/s. When reaching the tensile test temperature the tensile test is
performed during isothermal conditions with a constant pulling rate of 0.5mm/s which
corresponds to a strain rate of 0.1/s if we assume the deformation zone to be of the
same length as the heated zone i.e. 5mm.
Results from tensile tests are analyzed by the reduction of area (RA), ultimate tensile
stress (σb), elongation (lvdt) and strain to fracture (ε). The fracture surface with zero
ductility is used as indication of transition between ductile and brittle fracture. The
corresponding temperature is the transition temperature, TDB.

% 100
0
1 0


=
A
A A
RA (A1 is a mean value over three measurements)
0
max
A
F
b
= σ








⎛ ∆ +
=
0
0
ln
l
l l
ε

2. 3 Macrosegregat ion st udy
Macrosegregation occurs during solidification due to relative movement or flow of
segregated liquid and solid. There are numerous causes of fluid flow and solid movement
in casting processes. One reason for this movement of segregated liquid may be density
differences of the metal due to temperature or variations in composition. The hot liquid
metal becomes cooler close to the chill surfaces and its density increase causing
downward movement. Liquid being enriched by rejected solutes with higher density
compared to the bulk composition will flow downward and the opposite will happen
when low mass elements enrich the liquid. During ingot casting, the most common
macrosegregations are the positive, negative and channel segregations
8,9
. Positive segregation
means that the concentration of alloying element exceeds the average bulk concentration.
Negative segregation is instead a local lack of alloying element. The positive segregation is
often found at the top and is the result of segregated liquid flow toward the top,
10,11
and
the negative zone with more pure material at the bottom of the ingot is explained by
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6
sedimentation of equiaxed crystals formed in the bulk liquid.
12
Approximate at one third
from the surface the so-called A-segregates are found. They have the shape of pencil-like
channels, filled with alloy which contains high concentrations of the alloying elements.
Liquid jet streams melt the dendrite network allowing for channels to form and be filled
by enriched liquid flowing upward due to its lower density.
Drilling for chemical composition was made on ingots along the central axis and at
several cross sections at different heights. The results are plotted to obtain the
segregation pattern over C and S. Sulphur prints which reveal the S as dark marks are
used to analyse segregation channel placement and number density. These results are
used as in-data for numerical analysis.
2. 4 I nclusion st udy
2. 4. 1 I nclusion charact erist ics
Inclusions studied in this present work were analysed with emphasis on its
precipitation process and morphology. Our goal was trying to present a model on
inclusion formation based on measurements on liquid supersaturation, inclusion
characteristics and solidification process. Comparisons were made between different
crystal morphologies such as the columnar and equiaxed crystals and metallurgical
processing prior casting. Inclusions were characterized by use of scanning electron
microscopy (SEM) and element concentrations are measured by electron probe micro-
analysis (EPMA). From SEM images we determine type, shape and size distribution. By
use of energy dispersive scanning (EDS) we analyse inclusion chemistry. EPMA results
on concentration levels are used to study the precipitation process.
2. 4. 2 Elect ron Pr obe Micro- Analysis
Inclusions were investigated by Electron Probe Micro-Analysis, EPMA. This
technique has been known since late 1950. The first instrument was in place at The
Swedish Institute of Metals Research in the beginning of the 60’s. An electron beam is
focused to a 1 µm point by aid of electromagnetic lenses. The beam is used to penetrate
the surface (2 µm deep in steel materials) influencing the atoms to enable emitted x-ray
to analyse element specific wavelengths. Intensity is proportional to element amount. To
enable this type of measurement some modification must be made to the original SEM
equipment. Much higher, 500 – 1000 times, currents are used compared to conventional
SEM and sliding sample holder render possible surface scan. Calibration for each
element is made by mapping reference materials with known spectrums. One sample
with low element concentration and one sample with high element concentration are
used. One can choose to scan step wise in the range from 1×1 µm to 50×50 µm. The
micro distribution of selected elements are traced and transformed into a two
dimensional colour picture, each colour representing a certain amount. Each point
represents a mean value of the element concentration. All data about references,
coordinates and analyses are saved to be used for further investigation such as line-scan,
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7
mean values of certain structure areas or to better bring out low content of interesting
elements.
2. 5 I noculat ion in nodular cast iron
The same model on precipitation process used in the study on inclusions in steel
alloys can be used when evaluating the graphite formation during solidification of cast
iron. Precipitation of graphite nodules during solidification in nodular cast iron was
studied to better understand inoculation efficiency. Three different additives were used,
FeSi – Ca, FeSi – (Ca, Ce) and FeSi – (Ca, Ce, S, O). The same mirror furnace used for
hot tensile test was used to melt samples which solidify with a controlled cooling rate.
The samples melt by heat conduction while heating the graphite holder to about 1400
°C. All samples were cast in Zr2O-crucibles. A 250 mm long and 30 mm wide quartz
tube is placed around the specimen set-up and was continuously filled with argon gas to
protect it from oxidation. Quenching was made in water. Inoculation seeds were placed
at the bottom of the crucible before melting. A total of six tests from each alloy have
been studied. One from each alloy representing the total solidification interval. Five were
quenched within the solidification interval (1150 – 1010 °C). Maximum heating- and
cooling rate was set to 300°C and 60 °C/min respectively. Samples were kept for about
one minute at the maximum temperature. Temperature was sampled every 0.4 s and
measured in the centre of each sample. The time from completely liquid to start of
cooling is about 100 s for all tests. A maximum temperature of about 1375 – 1360 °C has
been recorded in the melt and is regarded as the inoculation temperature.
Samples were polished to a 3 um diamond paste finish and etched in 2-5% Nital, 2%
Pikrin or 5%Br – 95%Methanol solution. Studies were concentrated towards
microstructure, nodule count, nodule size distribution, inoculants efficiency and
inclusion characteristics. Nodule count and structure fractions were made by means of
point counting in 5×-magnifications. The inclusions are analysed by EDS in SEM.
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8
3 Result s
3. 1 Macrosegregat ion
Figure 3 shows a plot over the segregation ratio, C/C0 of carbon and sulphur in the
rectangular ingot. As to be expected the macrosegregations follow the well known
behaviour. In the figure, the concentration along three horizontal lines, representing
three height levels, from surface to centre are shown to the left, the centreline
segregation is shown in the middle and the position of each drill sample are shown to the
right. A sulphur print of the corresponding surface is shown in figure 4. In this ingot, an
increase of the segregation ratio is seen toward the top. The horizontal lines show that
the composition are even toward the surface at the mid to lower levels but has clearly
unstable segregation ratio towards the centre at the higher level, which is close to the
hot-top region. This instability coincides with the A-segregates seen in the sulphur print
in figure 4. At the bottom of the ingot a somewhat increasing negative segregation is
found.

-300 -200 -100 0
0
1
2
3
C
/
C
0
Top
-300 -200 -100 0
0.5
1
1.5
Middle
C
/
C
0
-300 -200 -100 0
0.5
1
1.5
Bottom
C
/
C
0
0.5 1 1.5 2 2.5
Centreline
C/C
0
-500 0 500
0
200
400
600
800
1000
1200
1400
1600
1800
Ingot width [mm]
I
n
g
o
t

h
e
i
g
t
h

[
m
m
]
C
S

Figure 3: Segregation ratio of S and C. Sample location is shown in the right figure.

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9

Figure 4: Sulphur print of vertical cross-section of rectangular ingot.
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10
3. 2 I nclusions charact erist ics
Three types of inclusions were found. To the left in figure 5 we see a duplex oxy-
sulphide inclusion where MnS has grown on Al2O3-nucleis, the centre picture is a MnS
inclusion and to the right in the figure we see the Al2O3. The inclusions are found in all
three materials but are different in type, shape and size. MnS found in the ingots are
classified as type III and I since they are sharp edged to spherical. Continuous cast
material contains type II MnS which are smooth and stringy. The oxides are all faceted.
Inclusion size and number density are found to be a function of crystal morphology.
Columnar structure favour precipitation of MnS and duplex oxy-sulphides. Equiaxed
crystal zone contains these inclusions too but to less extend together with pure Al2O3,
most of which are very small in size.


Figure 5: Duplex oxy-sulphide, pure MnS and pure Al2O3 in high-sulphur tool steel ingot

3. 3 I noculat ion in nodular cast iron
Nodule size measurements are presented in figure 6. The un-inoculated base iron
samples show a low number of large nodules. The number of nodules then increase at a
size of 20 – 25µm, and an additional increase is seen at a size of 5 – 10µm. Addition of
Ca and S – O treated inoculants lead to a more even distribution in comparison to
addition of FeSi – (Ca, Ce). FeSi – (Ca, Ce, S, O) which show a peak at 5 – 20µm is the
additive with most small sized nodules.
This is explained by formation of nodules at the beginning and at the end of
solidification. A support for this is found in the thermodynamic calculations [Fig 13a and
14a, supplement 3]. These show that MgO and MgS inclusions are formed at the
addition of Mg and nodules are nucleated on those. MgO and MgS inclusions are also
formed at the end of solidification acting as nucleation sites for graphite nodules.
Addition of inoculants containing Ce or other elements with high affinity to oxygen
shows a quite different nodule distribution. There is hardly any favourite size and the
distribution is more even [Fig. 6, supplement 3]. This might be explained by sulphides
and oxides are repeatedly formed during solidification process.
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11
0
10
20
30
40
50
60
5
-
1
0
µ
m
1
0
-
1
5
µ
m
1
5
-
2
0
µ
m
2
0
-
2
5
µ
m
2
5
-
3
0
µ
m
3
0
-
3
5
µ
m
3
5
-
4
0
µ
m
4
0
-
4
5
µ
m
4
5
-
5
0
µ
m
N
u
m
b
e
r

o
f

n
o
d
u
l
e
s
( Ca)
( Ca, Ce)
( Ca, Ce, S, O)
( pure base iron)

Figure 6: Nodule size distribution
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12
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13
4 Discussion
Results from supplement 1, 2 and 4 are to be considered as one investigation. We
made different types of experiments and analyses in order to investigate the origin of
defects such as segregation, crack formation and inclusions in cast ingots and continuous
cast slabs. The experiments are made on the same steel quality through out the work of
this thesis. Experiments were designed and tried out in order to achieve the correct
material data for further mathematical modelling.
The segregation pattern in the work made in supplement 2 follows the general view
on segregation behaviour. It is clear that the areas at which segregation channels are
found are prone to house high number density of inclusions. This is supported by
EPMA analysis over the area. The channel formation with remelting of the dendrite
network causing liquid enrichment with alloy elements being pushed from the solid into
the liquid with higher solubility enables the needed supersaturation to form these
inclusions. Results on macrosegregation and type of inclusions has been further analysed
in supplement 4 with emphasis on the inclusion formation process. The investigation
shows two different types of inclusions, (1) duplex inclusion where the core constitute an
oxide inclusion with a MnS outer shell and (2) pure MnS and Al2O3 inclusions in
different morphologies. It also shows that inclusion precipitation has crystal structure
dependence which is a function of solidification process. At higher solidification rates
the oxides incorporate into the solid and no small nuclei are available for MnS
precipitation.
The theoretical model used in supplement 3 and 4, based on well known segregation
models, analyses the precipitation behaviour of inclusions during solidification process.
The method to find at what point in the solidification process inclusions are expected to
precipitate are based on calculations with the Scheil and Lever rule in combination with
calculations on solubility products for nucleation. The theoretical results are compared
with experimental observations from EPMA and microstructure investigations. The
experimental result supports the calculations that Al2O3 inclusions precipitate before
MnS and thus acting nucleation sites for MnS. Results from the structure investigation of
Steel C also support this since this material contains less MnS and no oxides. This could
be an effect of the metallurgical treatment prior to casting.
In the same way as for the duplex inclusions found in the steel ingots the graphite
nodules precipitates on oxide nuclei. Pure base iron show uneven graphite nodule size
distribution compared to the iron inoculated with S and O treated additives. When
adding inoculants with Ce or elements with high affinity to oxygen the nodule size
distribution change from being uneven with a low number of large nodules to a more flat
distribution with hardly any favourite size. This is explained by repeatedly formed
sulphides and oxides during solidification process.
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14
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15
5 Conclusions
Ingot casting, continuous casting and inoculation experiments has been performed
with the intention to study crack formation, macrosegregation, inclusion characteristics
and the effect of metallurgy and solidification process. A crack prediction model used to
calculate temperature and elastic stresses was presented together with a model to
calculate the influence of the A-segregates in large ingots. The formation of inclusions in
steel alloys has been analysed by use of a new way to calculate the precipitation as
function of supersaturation and solidification process. The same model can also be
applied in the case with inoculation of cast iron.
Macrosegregation in the steel experiment in this study is similar to the general view of
segregation pattern, a negative segregation zone in the lower parts of the ingot and an
increasing composition toward the top. The primary source of the macrosegregation in
the ingot cast material is the transport of segregated liquid in the A-segregates. These
areas of saturated metal contain inclusions, mainly oxides and sulphides.
Inclusions are formed in the interdendritic areas where the liquid is highly enriched.
Sulphides and oxides are the most common types together with a duplex oxy-sulphide
where the MnS grow on oxide nuclei. Inclusion characteristics depend on crystal
morphology which can be related to casting process. Probably this is an effect of the
solidification rate, both in ingot and continuous cast processing. Calculations by aid of
homogeneous nucleation theory together with segregation calculations show that
precipitation of oxides start at a solid fraction of about 0.7 and the MnS not until a solid
fraction of 95% is reached. Results from structure analysis support the idea that oxides
act as nucleation sites for MnS precipitation. In the study on nodular cast iron it shows
that oxides present in the liquid promote nodule precipitation. During solidification re-
nucleation of oxides and graphite nodules result in a flat nodule size distribution with the
beneficial effect of less chill i.e. less problem with micro porosity.
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Clean Steel: Part One


Abstract:
Steel cleanliness is an important factor of steel quality and the demand for cleaner steels increases every
year. The so-called clean steel generally is the steel in which the content of impurity elements, such as
phosphorus, sulphur, total oxygen, nitrogen, hydrogen (including carbon sometimes) and inclusions are
very low. The improvement of steel cleanliness has therefore become a more and more important subject in
the development of ferrous metallurgical technology, and also an important task for the iron and steel
producers.




Steel cleanliness is an important factor of steel quality and the demand for cleaner steels increases every year.
The so-called clean steel generally is the steel in which the content of impurity elements, such as phosphorus,
sulphur, total oxygen, nitrogen, hydrogen (including carbon sometimes) and inclusions are very low. The
improvement of steel cleanliness has therefore become a more and more important subject in the
development of ferrous metallurgical technology, and also an important task for the iron and steel producers.
The demand for better mechanical properties of steels was urging steel producers to improve cleanliness of
their final products. In order to obtain the satisfactory cleanliness of steel it is necessary to control and improve
a wide range of operating practices throughout the steelmaking processes like deoxidant- and alloy additions,
secondary metallurgy treatments, shrouding systems and casting practice.
Due to the vague nature of the term "clean steel", some authors imply that it is more precise to refer to:
• steels with low levels of solutes as "high purity steels"
• steels with low levels of impurities that originate from the re-melting scrap as "low residual steels"
steels with a low frequency of product defects that can be related to the presence oxides as "clean steels".
It has been well known that the individual or combined effect of carbon [C], phosphorus [P], sulphur [S],
nitrogen [N], hydrogen [H] and total oxygen (T.O.) in steel can have a remarkable influence on steel properties,
such as tensile strength, formability, toughness, weldability, cracking-resistance, corrosion-resistance,
fatigue-resistance, etc. Also, clean steel requires control of non-metallic oxide inclusions and controlling their
size distribution, morphology and composition.
The control of the elements mentioned above is different for different performance demands. Those impurity
elements also vary with different grades of steel. Table 1 lists the influence of common steel impurities on steel
mechanical properties which means that some element is harmful to certain steel grades, but may be less
harmful or even useful to another steel grades.
For examples for IF steels, the content of carbon, nitrogen, total oxygen and inclusions should be as low as
possible in order to get good flexibility, high "r" value, perfect surface quality etc. In other hands the high quality
pipeline steel requires ultra low sulphure, low phosphorus, low nitrogen, low total oxygen content and a certain
ratio of Ca/S.
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Element Form Mechanical Properties Affected
S, O Sulfide and oxide inclusions
Ductility, Charpy impact value, anisotropy
Formability (elongation, reduction of area and bendability)
Cold forgeability, drawability
Low temperature toughness
Fatigue strength
Solid solution Solid solubility (enhanced), hardenability
Settled dislocation Strain aging (enhanced), ductility and toughness (lowered)
Pearlite and cementite Dispersion (enhanced), ductility and toughness (lowered)
C, N
Carbide and nitride
precipitates
Precipitation, grain refining (enhanced), toughness
(enhanced)
Embrittlement by intergranular precipitation
P Solid solution
Solid solubility (enhanced), hardenability (enhanced)
Temper brittleness
Separation, secondary work embrittlement
Table 1: Influence of typical impurities on mechanical properties
As we mentioned before, steel cleanliness depends on the amount, morphology and size distribution of
non-metallic inclusions. The inclusions generate many defects and many applications restrict the maximum
size of inclusions so the size distribution of inclusions in steel products is also important. For certain
applications where stringent mechanical properties are required the internal cleanliness of steel is very
important. Table 2 shows the cleanliness requirements for various steel grades.
Steel product
Maximum allowed impurity
fraction
Maximum allowed inclusion
size
IF steels
[C]≤30 ppm, [N]≤40 ppm, T.O.≤40
ppm
[C]≤10 ppm, [N]≤50 ppm

Automotive and deep-drawing
Sheets
[C]≤30 ppm, [N]≤30 ppm 100 µm
Drawn and Ironed cans
[C]≤30 ppm, [N]≤40 ppm, T.O.≤20
ppm
20 µm
Alloy steel for Pressure vessels [P]≤70 ppm
Alloy steel bars
[H]≤2 ppm, [N]≤20 ppm, T.O.≤10
ppm

HIC resistant steel sour gas tubes [P]≤50 ppm, [S] ≤10 ppm
Line pipes
[S]≤30 ppm, [N]≤50 ppm, T.O.≤30
ppm
100 µm
Sheets for continuous annealing [N]≤20 ppm
Plates for welding [H]≤1.5 ppm
Bearings T.O.≤10 ppm 15 µm
Tire cord [H]≤2 ppm, [N]≤40 ppm, T.O.≤15 10 µm
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ppm
Non-grain-orientated Magnetic
Sheets
[N]≤30 ppm
Heavy plate steels
[H]≤2 ppm, [N]=30-40 ppm, T.O.≤20
ppm
Single inclusion 13 µm
Cluster 200 µm
Wires [N]≤60 ppm, T.O.≤30 ppm 20 µm
Table 2: Cleanliness requirements for various steel grades
As Table 2 shows for sheets used for car body, carbon [C], nitrogen [N], and total oxygen (T.O.) are each
required to be very low. For sheets for tin plate application, total oxygen is not only needed below 20 ppm, but
the size of the non-metallic inclusions in steel has to be less than 20 µm.
For steel cord used in tires, the size of non-metallic inclusions in steel has to be less than 10 μm and even
smaller (5 µm) for TV shadow masks. For ball bearings, in order to improve their fatigue-resistance properties,
T.O. in steel has to be below 10 ppm and the size of non-metallic inclusions has to be less than 15 µm. For
meeting the specification of increasingly improved toughness for petroleum pipeline and of Hydrogen Induced
Cracking (HIC) resistance for the transport of sour natural gas, the sulphur [S] content in steel has to be
extremely low, less than 10 ppm.
Steel cleanliness is controlled by a wide range operating practices throughout the steelmaking processes.
These include the time and location of deoxidant and alloy additions, the extent and sequence of secondary
metallurgy treatments, stirring and transfer operations, shrouding systems, tundish geometry and practices,
the absorption capacity of the various metallurgical fluxes, and casting practices.
A one of the steelmaking process routes for the production of clean steels is outlined in Figure 1.

Figure 1: The process route for the production of clean steels


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Clean Steel: Part Two


Abstract:
Non-metallic inclusions, which are undesirable components of all steels, play an important role with respect
to their effect on the steel properties. Controlling inclusions in steel is closely connected with the concept of
"clean steel". The improvement in steel properties by control of non-metallic inclusions plays an important
part in defending the applications of steel against newer competitive materials.




Non-metallic inclusions, which are undesirable components of all steels, play an important role with respect to
their effect on the steel properties. Controlling inclusions in steel is closely connected with the concept of
“clean steel”. The improvement in steel properties by control of non-metallic inclusions plays an important part
in defending the applications of steel against newer competitive materials. The aims of the metallurgist are to
eliminate undesirable inclusions and control the nature and distribution of the remainder to optimize the
properties of the final product.
Generally, non-metallic inclusions in steel normally have a negative contribution to the mechanical properties
of steel, since they can initiate ductile and brittle facture. Among various types of nonmetallic inclusions, oxide
and sulphide inclusions have been thought harmful for common steels.
All steels contain non-metallic inclusions to a greater or less extent. The type and appearance of these
non-metallic inclusions depends on factors such as grade of steel, melting process, secondary metallurgy
treatments and casting of steel. Because of this, it is of particular significance to determine how pure the steel
is. The term steel cleanness is relative one, since even steel with only 1 ppm each of oxygen and sulfide will
still contains 10
9
-10
12
non-metallic inclusions per ton. From the viewpoint of “cleanness” all steels are “dirty”.
Non metallic inclusions in steel are the cause for dangerous and serious material defects such as brittleness
and a vide variety of crack formations. However, some of these inclusions can also have a beneficial effect on
steels properties by nucleating acicular ferrite during the austenite to ferrite phase transformation especially in
low carbon steels. According to definition, the non-metallic inclusions are chemical compounds of metal with
nonmetal which are present in steel and alloys like separated parts.
Classification of non-metallic inclusions
Non-metallic inclusions are divided by chemical and mineralogical content, by stableness/stability and origin.
By chemical content non-metallic inclusions are divided into the following groups:
• Oxides (simple: FeO, MnO, Cr
2
O
3
, TiO
2
, SiO
2
, Al
2
O
3
etc.; compound: FeOFe
2
O
3
, FeOAl
2
O
3
,
MgOAl
2
O
3
, FeOCr
2
O
3
etc.)
• Sulphides (FeS, MnS, CaS, MgS, Al
2
S
3
etc.; compound: FeSFeO, MnSMnO etc.)
• Nitrides (simple: TiN, AlN, ZrN, CeN etc.; compound: Nb(C,N), V(C,N) etc, which can be found in
alloyed steels and has strong nitride-generative elements in its content: titanium, aluminum, vanadium,
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cerium etc.)
• Phosphides (Fe
3
P, Fe
2
P etc.)
The majority of inclusions in steels are oxides and sulphides. Among various types of nonmetallic inclusions,
oxide and sulphide inclusions have been thought harmful for common steels. Usually, nitrides are present in
special steels (stainless steels, tool steels) which have elements with a strong affinity for nitrogen (e.g.
chrome, vanadium), which create nitrides.
Figure 1 shows sulfides and oxides of non metallic inclusion in steel.

Figure 1: Non-metallic inclusion in steel: oxides-dark gray and sulfides-light gray
By mineralogical content oxygen inclusions are divided into the following groups:
• Free oxides – FeO, MnO, Cr
2
O
3
, SiO
2
(quartz), Al
2
O
3
(corundum) etc.
• Spinels-compound oxides which are formed by bi- and tri-valent elements as a ferrites, chromites and
aluminates.
• Silicates which are presented in steel like a glass formed with pure SiO
2
or SiO
2
with admixture of
iron, manganese, chromium, aluminum and tungsten oxides and also crystalline silicates.
Depending on the melting temperature, in liquid steel non-metallic inclusions are in solid or liquid condition.
As mentioned above the majority of inclusions in steels are oxides and sulfides. Sulfides in steel have been
paid much attention because their treatment is an important problem in the steelmaking process. They affect
on the properties of the final products by their deformation during the steel working process; especially their
morphology has a significant effect on the steel properties.
According to analysis based on the steel ingots containing 0.01-0.15% S, the morphology of MnS can be
classified into three types:
1) Type I is a globular .MnS with a wide range of sizes, and is often duplex with oxides.
2) Type II has a dendritic structure and is often called grain-boundary sulfide because it is distributed as
chain-like formation or thin precipitates in primary ingot grain boundaries.
3) Type III is angular sulfide and always forms as monophase inclusion.
Most of the above mentioned sulfides are formed both during the process of secondary metallurgy or the
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solidification process. Recently, with the development of steelmaking technology, the sulfur concentration in
steel was lowered drastically. Also, the continuous casting technology of steels with higher cooling rate than
the ingot casting almost replaced the ingot casting.
So, the sulfides in the modern commercial steel are usually formed on solidification process or in solid steel
during the subsequent cooling process. For example, the Widmanstätten plate-like MnS
2
, is formed in solid
steel and Figure 2 shows the common morphology of MnS in conventional continuously casting steel,
including the globular duplex oxide–sulfide (particle A, B and C) and the Widmanstätten plate-like MnS
(particle D).

Figure 2: Typical duplex oxide–sulfide inclusion (particle A, B and C) and plate-like MnS (particle D) in
conventional continuous casting silicon steel.
Numerous examples of the effect of non-metallic inclusions on steel properties show the importance of the
behavior of the inclusions as well as of surrounding metal matrix during plastic working of steels. The aims of
the metallurgist are to eliminate undesirable inclusions and control the nature and distribution of the remainder
to optimize the properties of the final product.
An attempt by using program ABACUS was performed to model the behavior of slag inclusions and their
surrounding matrix material during hot rolling and hot forging of hardenable steels. It is shown that it can be
helpful for studying the behavior of inclusions, which is difficult or even impossible to obtain from a
conventional experiment.
Figure 3 shows the effective strain contour during plastic deformation. Three regions of strain concentration
(red) can be seen and a trihedral void (white region) close to the round inclusion is formed. The strain
concentrations arise at the inner surface of the matrix. Another interested thing is that two edges of the pore
tend to emerge and a bonding is formed. The difference in mechanical properties between the matrix and the
inclusion is found to be the primary reason to create a void. The weak bonding at the interface between the
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matrix and the inclusion seems to facilitate to open the void.
Figure 4 shows the effect of rolling temperature on the relative plasticity index during hot rolling of steels. The
relative plasticity index of inclusion increases while the rolling temperature rises. There exists a transition
region, where the relative plasticity index changes rapidly. This trend agrees with the existing experimental
results.

Figure 3: Void formation close to the inclusion.
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Figure 4: Effects of rolling temperature on the relative plasticity index.

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Clean Steel: Part Three


Abstract:
The presence of non-metallic oxide inclusions is a major cause of incompatibility between the attainable and
desirable level of cleanliness in many grades of commercial steel. Generally, inclusions degrade the
mechanical properties of the steel and thereby reduce the ductility of the cast metal and increase the risk for
mechanical and/or corrosion failure of the final product.




The increasing demand in recent years for high-quality steel products has led to the continuous improvement
of steelmaking practices. There is a special interest in the control of non-metallic inclusions due to their
harmful effect on the subsequent stages and their great influence on the properties of the final product.
Through the control of the amount, size and chemical composition of the inclusions it is possible to obtain a
final product of good quality. The control of the formation of non-metallic inclusions and the identification of
their constituent phases are of extreme importance for the obtaining of clean steels.
The presence of non-metallic oxide inclusions is a major cause of incompatibility between the attainable and
desirable level of cleanliness in many grades of commercial steel. Generally, inclusions degrade the
mechanical properties of the steel and thereby reduce the ductility of the cast metal and increase the risk for
mechanical and/or corrosion failure of the final product.
Oxide inclusions originate from two sources:
• residual products resulting from intentionally added alloying elements to deoxidize the molten steel
after oxygen treatment (endogenous or micro inclusions);
• products resulting from reactions between the melt and atmosphere, slag, or refractory (exogenous or
macro inclusions).
Among various types of nonmetallic inclusions, oxide and sulphide inclusions have been thought harmful for
common steels.
Alumina inclusions occur as deoxidation products in the aluminum-based deoxidation of steel. Pure alumina
has a melting point above 2000°C, i.e., these alumina inclusions are present in a solid state in liquid steel. The
addition of calcium to steel which contains such inclusions changes the composition of these inclusions from
pure alumina to CaO-containing calcium aluminates.
As it can be see from Figure 1, the, melting point of the calcium aluminates will decrease as the CaO content
increases, until liquid oxide phases occur at about 22% of CaO, i.e., when the CaO.2Al
2
O
3
compound is first
exceeded at 1600°C. The liquid phase content continues to increase as CaO content rises further and is 100%
at 35% of CaO. The minimum melting temperature for the liquid calcium aluminates is around 1400°C, i.e.,
such liquid calcium aluminates may be present in liquid form until, or even after, the steel solidifies.
Most grades of steel are treated with calcium using either a Ca-Si alloy or a Ca-Fe(Ni) mixture, depending on
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the silicon specification. This treatment is made after trim additions and argon rinsing.
In most melt shops the cored wire containing Ca-Si or Ca-Fe(Ni) injection system is used in the calcium
treatment of steel. The melting and boiling points of calcium are 839°C and 1500°C respectively. During
calcium treatment, the alumina and silica inclusions are converted to molten calcium aluminates and silicate
which are globular in shape because of the surface tension effect. The change in inclusion composition and
shape is known as the inclusion morphology control.

Figure 1: Binary system CaO-Al
2
O
3

The calcium aluminates inclusions retained in liquid steel suppress the formation of MnS stringers during
solidification of steel. This change in the composition and mode of precipitation of sulphide inclusion during
solidification of steel is known as sulphide morphology or sulphide shape control.
Several metallurgical advantages are brought about with the modification of composition and morphology of
oxide and sulphide inclusions by calcium treatment of steel, as for instance:
• To improve steel castability in continuous casting, i.e. minimize nozzle blockage
• To minimize inclusion related surface defects in billet, bloom and slab castings
• To improve steel machinability at high cutting speeds and prolong the carbide tool life
• To minimize the susceptibility of steel to re-heat cracking, as in the heat-affected zones (HAZ) of
welds
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• To prevent lamellar tearing in large restrained welded structures
• To minimize the susceptibility of high-strength low alloy (HSLA) linepipe steels to hydrogen-induced
cracking (HIC) in sour gas or sour oil environments. The Ca content in the final product can be controlled
within the range of 15 to 20 ppm
• To increase both tensile ductility and impact energy in the transverse and through-thickness
directions in steels with tensile strengths below 1400 MPa
When calcium is injected deep into the melt, the following series of reactions are expected to occur to varying
extents in Al-killed steels containing alumina inclusions:
Ca + O = CaO (1)
Ca + S = CaS (2)
Ca + (x+1/3)Al
2
O
3
= CaO·x Al
2
O
3
+ 2/3[Al] (3)
Depending on the steel composition, the manner of calcium adding in steel bath and other process variables,
there will be variations in the conversion of alumina inclusions to aluminates inclusions, the smaller inclusions
will be converted to molten calcium aluminates more readily than the larger inclusions.
Thermodynamically, if sulfur or oxygen is dissolved in the steel at moderate levels, or if Al
2
O
3
inclusions are
present in steel, calcium will react with oxygen or sulfur until the contents of reactants are very low (< 2ppm).
One of the critical questions is whether or not calcium added to steel will react with sulfur by reaction (2) and
form CaS or modify Al
2
O
3
to liquid calcium aluminates by reaction (3).
The formation of calcium sulfide can occur if calcium and sulfur contents are sufficiently high. Since calcium
has higher affinity for oxygen than for sulfur, the addition of calcium initially results in a more or less
pronounced conversion of the alumina into calcium aluminates until the formation of calcium sulfides starts as
the addition of calcium continues.
Calcium sulfides are solid at steelmaking temperatures and result in nozzle clogging similar to that caused by
alumina. As can be observed from the Figure 2, the conversion of alumina into calcium aluminates occurs until
all the inclusions in the steel are present only in liquid form.
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Figure 2: Change of inclusions composition during calcium additions
To prevent nozzle clogging in continuous casting by solid inclusions, calcium is added to steel to modify
inclusions and desulfurize the steel. Calcium will convert solid alumina (Al
2
O
3
) inclusions into lower melting
point calcium aluminates, which will help prevent the clogging of the casting nozzles. However, when calcium
is added to steel, it will also react with oxygen and sulfur and modify the sulfide inclusions. If the sulfur content
of the steel is high, calcium will react with sulfur forming solid CaS, which could clog up the continuous casting
nozzle.
The Figure 3 shows influence of calcium treatment on the type of inclusions formed and its relationship with
nozzle clogging.
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Figure 3: Influence of calcium treatment on the type of inclusions formed and its relationship with
nozzle clogging
Calcium treatment cannot be applied to all kinds of steel. For those with high requirement on formability, such
as automobile sheet, calcium treatment is not suitable, because this treatment causes the formation of calcium
aluminates inclusion which is hard. Therefore, for those kinds of steel, the method of improving molten steel´s
purity is usually taken to optimize castability. Through controlling carry-over slag from melting furnace,
deformation treatment of ladle slag, metallurgy in tundish, protective casting and other measures, purity of
steel is guaranteed and total oxygen content in molten steel decrease

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Control of Sulfur in Melts


Abstract:
Sulfur has a strong surface activity both in binary (Fe-S) and ternary (Fe-C-S, Fe-Si-S) alloys. It has been
concluded from the results of numerous studies that sulfur can exist in two forms in molten iron: in one case
it forms an interstitial solutions, and in other partially substitutional solutions. It has been found that the
activity of sulfur increase substantially when carbon and silicon are present in the melt. This explains why
pig iron can be desulfurized more readily than steel.




Sulfur (S) is a typical metalloid. The radius of sulfur atom is 1.05 Å. It easily acquires two electrons to form an
ion S
2-
. The coefficient of diffusion of sulfur in liquid iron is 0.74x10
-4
, 13x10
-4
, 1.9x10
-5
cm/s, according to
various experimental data. Sulfur has a strong surface activity both in binary (Fe-S) and ternary (Fe-C-S,
Fe-Si-S) alloys. It has been concluded from the results of numerous studies that sulfur can exist in two forms in
molten iron: in one case it forms an interstitial solution, and in other partially substitutional solutions. It has
been found that the activity of sulfur increase substantially when carbon and silicon are present in the melt.
This explains why pig iron can be desulfurized more readily than steel.
A good understanding of the desulphurization of hot metal and liquid steel has been developed in terms of
slag-metal reactions, based on a number of studies of the partition of sulfur between liquid slag and liquid iron.
These results show that a highly basic slag, high temperature and reducing conditions enhance
desulphurization via slag-metal reactions.
Sulfur Equilibrium between Liquid Iron and Slag
The desulphurization of liquid iron with slag may be examined on the basis of the following reaction (1), in
which the equilibrium constant can be expressed by equation (2).
[S] + (O2-) = (S2-) + [O] .......... (1)
log K
1
= a
s
2-
. a
o
/ a
s
. a
o
2-
.......... (2)
where,
• a
o
, a
s
: the activities of oxygen and sulfur in liquid iron, respectively
• a
o
2-
, a
s
2-
: the activities of oxygen and sulfur ions in slag, respectively.
The sulfur partition ratio between metal and slag is given by equation (3) according to reaction (1).
L
S
= (wt%S) / [wt%S] = K
1
• a
o
2-
• f
s
/ a
o
• f
s
2-
.......... (3)
where,
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• f
s
, f
s
2-
: the activity coefficients of sulfur in liquid iron and slag, respectively.
Since the values of K
1
, a
o
2-
and f
s
2-
cannot be determined experimentally, the sulfide capacity is defined as
equation (5) on the basis of reaction (4) and is utilized for the examination of desulphurization in iron and steel
making processes.
½ S
2
+ (O
2-
) = (S
2-
) + ½ O
2
.......... (4)
C
S
= (wt%S) • (P
O2
/ Ps)½ = K
4
a
o
2- / f
s
2-
.......... (5)
where,
• P
O2
and P
s
are the oxygen and sulfur partial pressure in atm;
• K
4
the equilibrium constant of reaction (4).
In order to calculate the value of C
S
, the equilibrium constants of reactions (6) and (7) are substituted into
equation (5), and equation (8) is obtained.
½ O
2
= [O] .......... (6)
½ S
2
= [S] .......... (7)
log C
s
= log (wt % S) a
o
/ a
s
+ 936 / T-1.375 .......... (8)
By the use of the interaction coefficients of sulfur and oxygen in liquid iron, the values of C
S
can be calculated
from equation (8).
As an illustration, the calculation of sulfide capacity (C
S
) has been given for CaO-MgO-Al
2
O
3
-SiO
2
ladle slags.
In order to examine the relationship between C
S
and composition of slag, the following relationship is assumed
to hold at certain temperatures.
log C
S
= α (N
CaO
+ K
MgO
• N
MgO
+ K
Al2O3
• N
Al2O3
+ K
SiO2
• N
SiO2
)+ β .......... (9)
where:
• α, β: the constants
• Ni, Ki: the mole fraction and the lime equivalent coefficient of i-component in the slag phase,
respectively.
At 1600°C, the values of K
MgO
, K
Al2O3
and K
SiO2
determined by trial and error are 0.1, -0.8 and -1.0,
respectively. As shown in Figure 1, there are linear relations between log C
s
and (N
CaO
+ 0.1 N
MgO
– 0.8 N
Al2O3

– N
SiO2
) at 1575, 1600 and 1650°C.
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Figure 1: Plot of the log C
s
against N
CaO
+ 0.1N
MgO
– 0.8N
Al2O3
– N
SiO2
at 1575, 1600 and 1650°C
The three lines obtained by the method of least squares are shown in the figure. The intercepts of the lines
were determined by the use of the slope at 1600°C because the most runs were done at this temperature. The
following equation was obtained as a function of temperature.
log C
S
= 3.44 (N
CaO
+0.1N
MgO
– 0.8N
Al2O3
– N
SiO2
) - 9894 / T+2.05 .......... (10)
The observed values of log C
S
with the correlation coefficient (R) of 0.99 and the standard deviation (σ) of
0.044 can well be expressed by the above equation.
On the other hand, log L
S
may be expressed by the following general equation derived from equations. (3), (8)
and (10).
log L
S
= α ∑ K
i
•N
i
- log [wt%O] - β .......... (11)
where,
• ∑ K
i
•N
i
= N
CaO
+0.1N
MgO
– 0.8N
Al2O3
– N
SiO2
.
The experimental data were arranged by the method of least squares according to equation (11) and the
following relationship was obtained.
log L
S
= 3.44 ∑ K
i
•N
i
- log [wt% O] - 10 980 / T+3.50 .......... (12)
Relationship Between Sulfide Capacity and Theoretical Optical Basicity
Duffy and Ingram defined the theoretical optical basicity (Λ) as follows:
Λ = ∑ (x
i
/ f
i
) .......... (13)
where, x
i
, f
i
: the equivalent cationic fraction and the basicity moderating parameter for the constituent cation i,
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respectively.
It was verified by them that f
i
can be expressed by the Pauling's electronegativity x
i
as follows:
f
i
=1.36 (x
i
-0.26) .......... (14)
It was also found by Duffy and Ingram that log C
S
are linearly correlated to the theoretical optical basicity.
As an illustration of the above mentioned the experimental results performed on ladle CaO-MgO-Al
2
O
3
-SiO
2

slags has been given. The values of log C
S
are plotted against the optical basicities at 1575, 1600 and 1650°C,
as shown in Figure 2.

Figure 2: Plot of log CS against theoretical optical basicity Λ
The slopes and intercepts of the lines were determined by the method of least squares, and the following
linear relationship was obtained as a function of temperature.
log C
S
= 14.20Λ - 9 894 / T -7.55 .......... (15)
As described above, it can be seen that both the sum of lime equivalent and the optical basicity are able to be
used as parameters for the representation of sulfide capacity. From the relationship between these two
parameters, the linear equation (16) from regression was obtained.
Λ = 0.24(N
CaO
+ 0.1N
MgO
– 0.8N
Al2O3
– N
SiO2
) + 0.67 .......... (16)
The correlation coefficient (R) is larger than 0.99, and the standard deviation (σ) is smaller than 0.01. This
shows that the two parameters have almost the same character for the representation of sulfide capacity of
slag.
Equilibrium of Oxygen Partition between Metal and Slag
It is well known that the oxygen potential exerts a large influence on the sulfur partition between metal and
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slag. The equilibrium of reaction (17) was determined by the use of the value of the equilibrium constant (18)
reported in literature.
(FeO) = [Fe] + [O] .......... (17)
log K
17
= log a
o
/ a
FeO
= -6 150 / T + 2.604 .......... (18)
Equation (18) may be modified to the following equation.
log [wt%O] = log N
FeO
+ log γ
FeO
- log f
o
- 6 150 / T + 2.604 .......... (19)
where γ
FeO
is the activity coefficient of FeO on the basis of mole fraction.
Since log γ
FeO
is a function of temperature and slag composition, log [wt%O] can be expressed by an equation
including the term of log N
FeO
, then the following relationship was obtained.
log [wt%O] = 0.905 log N
FeO
-0.15 ∑ K
i
•N
i
- 6 340 / T + 3.115 .......... (20)
where, ∑ K
i
•N
i
= N
CaO
+ 0.1N
MgO
– 0.8N
Al2O3
– N
SiO2
.
As shown in Figure 3, the observed values of log [wt% O] agree well with the values calculated from the
equation (20). By substituting equation (20) into equation (12), equation (21) is derived:
log LS = 3.59 ∑ K
i
•N
i
-0.905 log N
FeO
– 4 640 / T + 0.385 .......... (21)
The above equation can conveniently be used for the estimation of the sulfur partition between liquid iron and
slag in which the oxygen content in liquid iron is not analyzed. Next, the values of γ
FeO
calculated from the
equation (19) were arranged by the way similar to that described previously, and the following relationship was
obtained.

Figure 3: Comparison of the observed log [wt%O] with calculated log [wt%O] from the equation (20)


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Some Fundamental Steps in Thermomechanical Processing
of Steels* .
By Imao TAMURA**
Key words: ~hermomechanicalprocetsing; steel; deformation o f austenite;
restoration process; phase transformation; microalloying; f erri t e grai n re-
Jinement.
I. Introduction
Thermomechanical processing is a treatment of
which plastic deformation is introduced into the heat
treatment of steel. We can find many treatments in
such processes. But controlled rolling and acceler-
ated cooling, and the ausforming or deformation-
quenching are representative and are used in practical
production.
I n controlled rolling, the austenite (y) is work-
hardened with plastic deformation (rolling) in high
strain rate at elevated temperatures, and then air
cooled to transform to ferrite (a). Sometimes, work-
hardened austenite is cooled acceleratedly to take fine
ferrite grains in steel plate.
-
In the ausforming, work-hardened austenite is
quenched to room temperature. We can take the
ausformed martensite which increases its strength and
not decrease its toughness. The ausforming is not so
popular in practice but the deformation-quenching is
getting to be popular. The martensite in the defor-
mation-quenching looks like as usual martensite. But,
this martensite has a little bit of fine facet size be-
cause it is formed from smaller austenite grains than
usual austenite. This process can abridge to ration-
alize the heat treatment process of steel.
As fundamental steps in thermomechanical proc-
True strain
tn
3
Fig. 1. Schematic illustration of two types of true stress-
true strain curves accompanying the steady state
deformation at elevated temperatures.
( a)
dynamic recovery
essing of steels, we can point out that:
1)
The deformation and restoration processes of y
during and after hot rolling.
2)
The kinetics of y to a transformation and grain
size of a.
3)
The effect of cooling rate on transformation of
work-hardened y to a, and grain size of a.
4)
Structure of martensite in ferrous alloys.
5)
Structure and properties of martensite formed
from work-hardened y.
6)
Hardenability of work-hardened y and recrystal-
lized y.
I will explain on these processes based on our re-
search results.
(b) dynamic recrystallization
II. Deformation Behaviors of Austenite during
and after Hot Working
I . Restoration Process during Hot Deformation of Auste-
I t is well known that the deformation behavior of
austenite at elevated temperatures is a dynamic re-
crystallization type. Figure 1 shows schematically
both types of dynamic recovery type and dynamic
recrystallization type.
I n the case of a dynamic recrystallization type,
since the rate of softening due to recovery is slow, the
work-hardening can not be balanced only by dynamic
recovery even at high temperatures, and the disloca-
tion density is still gradually increased with strain,
and finally the recrystallization starts to occur during
deformation. The true stress is lowered beyond the
peak stress by the occurrence of dynamic recrystal-
lization and reaches a certain steady state stress
level at which the work-hardening and softening due
to recrystallization occurring repeatedly are balanced.
The dynamic recrystallization starts at the strain of
around 0.78, (E,: the strain showing the peak stress).
In Fig. l(b), the strain range up to about 0 . 7 ~ ~ is
the work-hardening region, the strain range between
about 0.78, and 8, (the strain at which the steady
state deformation starts) is the range of partially
dynamic recrystallization, and the strain range after
E , ~ is the range of steady dynamic recrystallization.
Austenite in steels belongs to this type. In a-Fe (fer-
rite), since the recovery occurs very fast, the restora-
tion is performed mainly by dynamic recovery. The
peak stress (a,) and the steady state stress (a,) in the
dynamic recrystallization type change with the Zener-
*
Based on the Special Lecture delivered by Prof. Tamura in commemoration of his receiving Nishiyama Medal in the 113th ISIJ
Meeting, April 2, 1987, at The University of Tokyo in Tokyo. Manuscript received on May 18, 1987. 0 1987 ISIJ
* * Professor Emeritus, Kyoto University; Technical Advisor, Sumitomo Metal Industries, Ltd., Nishinagasu-hondori, Amagasaki 660.
Special Lecture ( 763 )
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[ 764 ) Transactions ISIJ, Vol. 27, 1987
Hollomon parameter (2). Z is expressed by
where, i: the strain rate (s-l)
I? : a gas constant (J/mol)
Q:
the activation energy for deformation (J/
mol)
7: temperature (K).
a?,, ep, gs and E , are increased with increase in Z (i.e.,
with increase in i or decrease in 7).
Figure 2 shows the change in optical microstructure
with strain in Fe-31%Ni-0.3%C austenitic alloy
which was tensile deformed at 1 273 K (1 000°C) at a
strain rate of 1.7 x 10-2/s. Figure 2(a) is the austenite
structure before deformation. Austenite grains are
equiaxed and their boundaries are smooth and planer.
Many annealing twins exist in austenite grains. When
deformed slightly (E= 0.08), as shown in Fig. 2 (b), the
grain boundaries become finely serrated and the bulg-
i n g ~ of grain boundary are observed as indicated by
the arrows. At the strain slightly after E,, many small
grains are newly formed along the austenite bound-
aries as shown in Fig. 2(c). It is characteristic that
these newly formed grains hardly contain annealing
twins. Furthermore, some of the initial austenite
grains becomes larger by the strain-enhanced coarsen-
ing. Figure 2(d) shows the structure in the range of
steady state deformation at which the work-hardening
and the dynamic recrystallization softening are bal-
anced. This structure consists of several grains cor-
responding to various stages of recrystallization, i.e.,
from small grains which have just started to recrys-
tallize to fairly large grains which have been subjected
to deformation after the finishing of recrystallization
and are the work-hardened state just before the next
recrystallization. I n the stage of steady state defor-
mation, the recrystallization occurs repeatedly during
deformation. Dynamic recrystallized grains contain
a few annealing twins at low Z but scarcely contain
them when Z is high.
I n the same way as the static recry~tallization,~) it
has been observed that there are two main mech-
anisms for dynamic recrystallization, i.e., the bulging
mechanism and the nucleation-growth mechanism.
Dynamic recrystallization becomes easier to take
place when the initial grain size (do) of austenite is
smaller. Therefore, in the case of fine initial grain
size, c p and E, become small even at the deformation
under the same Z condition. However, a,, and a , are
independent of do. The average size (d) of dynam-
ically recrystallized grains is the only function of Z
and is expressed by the following equation,')
where, A, : material's constant.
A is larger for C-steel than for alloy steels, especially
small for Nb-containing steel and high alloy steel. p
is about 0.3-0.4 for all steels. It should be noted
that d is independent of do.
2. Static Restoration Process during Holding Right after
Hot Deformation
When the hot deformation is finished at the work-
hardening stage, the work-hardened austenite is sof-
tened by the usual static recrystallization during iso-
thermal holding after deformation. However, if the
strain is too small, the recrystallization can not occur
and only the recovery takes place. On the other
hand, when specimens are isothermally held after de-
formation to the range of the steady state deformation,
in which the dynamic recrystallization has occurred,
the recrystallization and the grain growth can succeed
to occur continuously during holding after hot defor-
mation. Such a recrystallization is called a meta-
dynamic or postdynamic recrystallization. Namely,
the dynamically recrystallized structure is further
softened by the metadynamic recrystallization. When
specimens are deformed to the range of (11) in Fig.
(a) Before testing (E=O)
(b) € =0.08
(c) e=0.24
(d) &=0.40
Pig. 2. Optical micrographs showing tlie formation process of dynamically recrystallized austenite in Fc-31Ni-0.3C
austenitic alloy deformed at 1 OOO°C, 1.7 x 10-2/s.
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l (b) in which the work-hardened austenite and dy-
namically recrystallized austenite have coexisted, the
static recrystallization occurs in work-hardened aus-
tenite and the metadynamic recrystallization occurs
in dynamically recrystallized austenite at the same
time.
I n case of rolling by hot strip mill in which slabs
are rolled by several passes, the static restoration proc-
ess occurring during interval between rolling passes
has great influence on the deformation behavior of
next rolling pass. If the softening due to the static
restoration is not completed during interval between
rolling passes, the work-hardening is successively ac-
cumulated by the subsequent rolling passes.
Fraction of softening (X) occurring during iso-
thermal holding right after hot deformation can be
evaluated by the two-step deformation test from the
following e q~a t i on, ~)
where, cr,,,: the flow stress immediately before un-
loading
c ~ , , ~ : the yield stress on reloading after hold-
ing the specimen for various periods of
time (At)
u,,, :
the initial yield stress.
As an example, the change in the fractional softening
(X) with the holding time (At) in Fe-31 %Ni-O.S%C
austenitic alloy is shown in Fig. 3. Specimens were
tensile deformed at 1 373 K (1 100°C) at a strain rate
of 4 x 10-2/s to E = 0.18 (work-hardened austenite) and
e= 1.0 (completely dynamically recrystallized auste-
nite), respectively, and then isothermally hild for
various periods of time. The change in average aus-
tenite grain size with At is also plotted in Fig. 3.
Microstructural changes during isothermal holding at
1 373 K (1 100°C) are shown in Fig. 4 and Fig. 5.
As shown in Fig. 4 (~=0. 18), work-hardened austenites
are slightly elongated along the tensile direction (Fig.
4(a)). The austenite hardly changes by holding for
1 s (Fig. 4(b)), although the softening occurs to some
extent by the static recovery as can be seen in Fig. 3.
However, when specimens were isothermally held for
4 s (Fig. 4(c)), fine austenite grains which are form-
ed by static recrystallization are partially formed
mainly along the deformed austenite grain boundaries
and the static recrystallization is completed by the
holding of 15 s (Fig. 4(d)). Annealing twins in static
recrystallized austenites are gradually developed with
increase in holding time. By holding for 40 s, recrys-
tallized austenite grains are coarsened (Fig. 3). When
the austenite was much more heavily deformed under
higher Z condition (work-hardened), the static re-
crystallized austenite grains become much finer as
shown in Fig. 6. As shown in Fig. 5 (a=1.0), dy-
namically recrystallized austenites are characterized
by irregular grain boundaries, a low density of an-
nealing twins and the mixed grain size. With in-
crease in holding time, austenite grain boundaries
become fairly straight and austenite structure becomes
almost equiaxed grains, and furthermore, the density
of annealing twins is increased. This is the typical
microstructural change occurring during metadynam-
ic recrystallization process. Metadynamic recrystal-
lization is completed by the holding for about 30 s in
the case of Fig. 5, and the usual grain coarsening oc-
curs by further holding. The grain size right after
the completion of metadynamic recrystallization is
smaller, as the grain size of dynamically recrystallized
Hdding time. A t (s)
Fig. 3.
Change in fraction of softening (a) and austenite As-deformed ( At = 0 S) (b) At = 1 s (c) At = 4 s (d) ~t = 15 s
grain size (b) with the isothermal holding time of Fig. 4. Change in optical microstructure of work-hardened austenite (de-
work-hardened austenite and dynamically recrystal- formed at 1 100°C, t = 4.0 x 10-2/s, c ~0 . 1 8 ) during isothermal holding
lized austcnite in Fe-31Ni-0.3C austenitic alloy. at 1 100°C for At in Fe-31Ni-0.3C austcnitic alloy.
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(a) AS-deformed ( ~ t = O s) (b) At = 1 s (c) At=2 s (d) At=30 s (a) Work-hardened austenite (detormed at 900°C,
Fig. 5. Change in optical microstructure of dynamically recrystallized austenite e=3/s, ~ z 1 . 0 )
(deformed at 1 100°C, d = 4.0 x 10-Z/s, E = 1 .O) during isothermal (h) Static recrystallized austenite (isothermally
holding at 1 100°C for At in Fe-31Ni-0.3C austenitic alloy. held at 900°C for 50 s of structure (a)
Fig. 6.
Optical micrographs showing the static recrystal-
austenite is smaller.
lization occurring during isothermal holding after
heavily work-hardened austenite in Fe-31Ni-0.3C
3. Efect of Alloying Elements on the lietardation of Re- austenitic alloy.
crystallization5)
Table 1. The values of n and m in Eq. (4) for varlous
The effect of alloying elements on the restoration
transformation conditions.
process during or after hot deformation is very im-
portant. Micro-addition of Nb or Ti acts as a re-
Mechanism Site saturation
Nucleation and
markable retardation effect on recrystallization due to
growth
-- - - - - - --
the suppression of grain boundary migration. The Site n m n m
suppression of grain boundary migration due to micro-
Grain surface 1 1 4 1
alloying is caused from (1) the solute dragging effect
Grain edge 2 2 4 2
due to segregation of alloying elements to the bound- Grain corner 3 3 4 3
aries, or (2) the pinning effect due to precipitates of
carbonitride of alloying elements at grain boundaries.
For example, Mo segregates to the austenite grain
x = l - exp [ - k ( ~ ) $ ] ..... . . . . . . . . . . (4)
boundaries, resulting in the suppression of grain
boundary migration. Even Nb micro-addition, at where, X: the transfbrmed fraction
high 1, it can retard the recrystallization by dragging
effect. But, usually, Nb and Ti are precipitated as
fine carbonitride particles and these precipitates sup-
press the grain boundary migration by the pinning
effect.
III. Transformation Kinetics and Grain Size of
Ferrite Transformed from Austenite
I . Isothermal Transformation Kinetics of Austenite
When the ferrite or pearlite Sorms from austenite
by isothermal holding below the transformation tem-
perature, these nuclei form preferentially at the prior
austenite grain boundaries. We expressed as Eq. (4)'3
that their transformation kinetics include the effect of
austenite grain size, by modification of Johnson-Mehl
equation.
t : the isothermal holding time
d: the austenite grain size
k ( 7 ) :
the rate constant which depends only
on transformation temperature and di-
rectly corresponds to the C-curve of
TTT diagram (isothermal transforma-
tion diagram).
The values oS the exponent m and n are listed in Table
1.6) These values depend on both the transformation
mechanism and type of nucleation site. Here the
transformation which progresses with nucleation and
growth over almost entire range of transformation is
called " nucleation and growth ". The transforma-
tion where all the nuclei are nucleated at the early
stage in the reaction and the progress of transforma-
tion is controlled mostly by their growth is called
" site saturation ". An austenite grain is assumed to
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( 767)
be a tetrakaidecahedra, and the nucleation sites at
austenite grain boundary can be classified into sur-
faces, edges and corners as are shown in Fig. 7.697)
Of course the actual nucleation sites are not limited to
any one of such types, and the value of m would be
the weighted average of the various nucleation sites
and not always be an integer.
According to Umemoto and Tamura,e) the values
of n and m, and transformation modes were experi-
mentally shown as in Table 2. I t is mentioned in
Table 2 that the mode of y +a transformation is site
saturation, but i t means the large number of nuclea-
tion o f a would occur at the beginning of transforma-
tion, which would not be real "site saturation ".
Sometimes the nucleation site is varied by supercool-
ing (accelerated cooling). It seems that the nuclea-
tion site of a is moved gradually from edge to surhce
by decrease in transformation temperature with cool-
ing rate, as described later.
2. Continuous Cooling Transformation Kinetics of Austenite
Scheils) considered the case where the austenite is
cooled continuously through its transformation tem-
perature. He assumed that austenite consumes its
fractional nucleation time and when the sum of a
number of such fractions equals unity, the transfor-
mation starts, i.e.,
Fig. 7. Schematic diagram of austenite grain as a tetra-
kaidecahedra and showing 3 types of nucleation
sites offerritc.
'Table 2. The values of r2 and m for various trans-
formation modes.
Transformation n m Nucleation
-
Pearlite 4 2 Edge nucleation
Nucleation and growth
1:errite 1 1 Surface nucleation near
Site saturation
Bainite 4 0. 6 Grain boundary,
Inside grain
Now extend this Scheil's additivity rule to the
entire range of transformation. I n this case the incu-
bation time ( ~ ( 7 ) ) is replaced with the time required
for the reaction to reach a certain fractional comple-
tion X by isothermal holding at temperature T. If
we combine Eq. (5) with Eq. (4)
where, Q( T) = -dT/dt: a cooling rate.
This equation expresses the transformed fraction at
temperature T during cooling from austenite condi-
tion with a cooling rate Q(T).6t9) Furthermore, from
Eqs. (4) and (6) we obtain
1 Te K(T1)1/7~
t ( 7 ) = - J - - - d T ' = t., ...... (7)
K T ) T Q(T' )
This equation tells that the fraction transformed by
cooling from 7, to T with cooling rate Q( T) is equal
to that obtained by the isothermal holding at tem-
perature T for time t ( 7) . Thus we call t ( T) as an
equivalent cooling time, t,,. t,, means the isothermal
holding time which gives the equivalent transformed
fraction with continuous cooling. The curve pro-
duced by the successive plot oS such t,, at each tem-
perature during cooling with cooling rate Q( T) will
be called an equivalent cooling curve.'O) The trans-
formation behavior for a given cooling curve can be
predicted from the TTT diagram by plotting such
curve on a TTT diagram.
3. Ferrite Grain Size Transformed from Austenite
1. Expression for Ferrite Grain Size (Isothermal)
I n general, ferrites nucleate at austenite grain
boundaries and grow into austenite grains. The
grain size of ferrite formed from austenite is directly
related with the process of transformation.") The
nominal ferrite grain diameter D, can be expressed
with the total number of ferrite grains uncleated
throughout transfbrmation per unit volume of auste-
nite, n,, as12)
where, I : nucleation rate per unit volume oS aus-
tenite
X: volume Sraction transformed
Thus the problem of obtaining the exprcssion for fer-
rite grain size is the problem of how to express n,>.
When ferrites nucleate at the austenite grain bound-
ary surfaces, they grow as ellipsoid with the aspect
ratio of 3: 113) as shown in Fig. 8. The total number
of rerrite grains nucleated per unit area of austenite
grain boundary surface is
9
n, = I,J; exp (-Tzaz~stz dt = - -
) 3:2-(':')
Nuclcation and growth
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ferrite gr a i n
gr ai n boundory
r=3Cl(t- 2)
Fig. 8. Schematic drawing of a ferrite grain nucleated at
austenite grain boundary surface.
where, I, : the nucleation rate per unit area oL aus-
tenite grain surface
a : parabolic rate constant for thickness.
The ferrite grain size D, is given as
where, Sg. b: the austenite grain surface area per
unit volume
and can be expressed by austenite grain diameter, D,,
as
Substituting Eqs. (10) and (12) into Eq. (l l ), the
ferrite grain size and the y / a transfbrmation ratio can
be expressed as
and
In the above derivation it was assumed that the
nucleation rate and the parabolic rate constant of
growth are time independent and one nuclei grows
and forms one grain.
Similarly the D, and y / a transformation ratio in the
case of homogeneous and grain edge nucleation has
been obtained asl1)
where, I h : the homogeneous nucleation rate per unit
volume
I, :
nucleation rate per unit length of auste-
nite grain edge.
I t should be noted that the equations introduced
above indicate that ferrite grain size and y/a trans-
formation ratio depend on the ratio of square root of
the nucleation rate to the parabolic rate constant in
all three types of nucleation sites. Furthermore Sor
grain boundary nucleation a small austenite grain
leads to a small ferrite grain. The effect of austenite
grain size on ferrite grain size depends on the type of
nucleation site, and it becomes large in the following
ascending order: homogeneous, grain surSaces, and
grain edges.
I t should be noted that the grain refinement on
austenite turns out to be less effective in ferrite grain
refinement. For instance in the case of grain surface
nucleation D, is proportional to D',I3 in Eq. (13).
This means that when D, is reduced to 118 of the ini-
tial, D, would be reduced only into 112.
Figure 914) shows experimental results of isothermal
transformation in a steel (0.2 % C, 0.0016 0/, B). The
steel was austenitized between 1 000 and 1200°C to
change its austenitic grain size from about 53 to 88
pm, and then transformed at 700, 680 and 660°C into
Ferrite. The results are recognized as the dependent
of y-grain diameter that a nucleates mainly at grain
edges at 700°C, at grain edges and surfaces at 680°C
and at the surfaces at 660°C.
2. Estimation of Ferrite Grain Size Formed by Continu-
ous Cooling Transformation
It can be assumed ferrite nucleates preferentially at
austenite grain surfaces by supercooling. A continu-
ous cooling transformation can be considered as the
sum of short time isothermal holdings at successive
temperatures as is schematically shown in Fig. 10.
During cooling, ferrite grains are nucleated and
grow at each temperature with the corresponding
nucleation and growth rates, as is schematically shown
in the Fig. 10 (bottom). During ferrite transforma-
tion carbon enriches in retained austenite, however,
since ferrite nucleation occurs mostly in the early stage
of transformation, it can be assumed that both the
nucleation and growth rates of ferrite are a function of
an instantaneous temperature only and not a function
of thermal history.
Based on this assumption, the number of ferrite
nuclei (N,) nucleated at temperature I, during cool-
ing, N, is given as Eq. (16).
where, Q( T) (= -dT/dt) : a cooling rate.
Ferrite grains once nucleated grow thereafter with a
corresponding growth rate at each temperature during
cooling. Thus, at temperature T, the radius of a fer-
rite grain on an austenite grain surface nucleated at
temperaturc T,, is given as Eq. (1 7).
The austenite grain boundary area occupied at tcm-
pcrature 7 by a ferrite grain nucleated at temperature
T, is given as Eq. (18).
I t will be convenient to use the concept of extended
area which is the sum of the areas of austenite grain
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( 769 ]
Au s t e n i t e Gr ai n Size
Fig. 9. An example of D,- or D,/D,,-D, rclationsllip for
S15C steel.
surface occupied by ferrite grains, assuming that fcr-
rite grain never stop growing and that ferrite grains
keep nucleating at the same rate during transforma-
tion as well as on untransformed austenite grain sur-
faces. The extended grain boundary area occupied
by all the ferrite grains nucleated at T, during cool-
ing is given as Eq. (1 9).
Thus the grain boundary arca fraction occupied by
the ferrite grains nucleated during cooling horn A3( T, )
to T is givcn by Eq. (20).
{J:$?&; dl-' d T , ............
1 1 (2 0)
The total number of ferrite grains nucleated per unit
area of austenite grain boundary surfacc is given by
Eq. (21).
Ferrite grain size is given as Eq. (22).
o ~ * ~ ~ ~ * TI T2 T3 Tl,
d ( h ) d ( T 2 ) d( T3) ~ ( T L )
I s( T ) I s(T2) Is(T3) Is(TL )
Fig. 10. Diagrams to explain the relation between iso-
thermal and continuous cooling transformation
and schematic drawing showing the formation
process of ferrite during continuous cooling.
673 773 873 973 1073 1173
TEMPERATURE, K
Fig. 11. Calculated parabolic rate constant and nucleation
rate I, as a function of' temperature for the steel
studied. (S15C)
where, Sg.,,(=4/(dn D,)): the austenite grain surface
area pcr unit volume.
From these equations, ferrite grain s i ~ e can be cal-
culated.
I t is fairly difficult to estimate of I , ( T ) and tt(T)
by some kinds of calculation, but it is not impossible.
By using several assumptions and h y p o t h e s i ~ , ~ ~ ' ~ - ~ ~ )
I , ( T ) and a ( T ) are roughly calculated as shown in
Fig. 1 lZ4) as a function of transformation tempera-
ture. I n this figure, I , shows a maximum value at
913 K (640°C) and n shows a maximum value at
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873 K (600°C) fbr S15C steel (0.15 % C, 0.4 % Mn).
Figure l2Z4) shows a comparison of calculated
values and experimental values for C15C steel. Wc
can get a roughly agreement, that is, a-grain size is
getting smaller with cooling rate increases. The Sor-
mulations are :
Dtv = Q-0. 17(D, )1' ~cal ~ul at ~d) ... ......... ...... (23)
Do = 5.7Q-0.2'3(D,)0.46 (experimental) . . . . .. . . .(24)
Figure 1324) shows experimental results.
IV. Ferrite Grain Refinement by Work-harden-
ing of Austenite
I . Ferrite Nucleation in Deformed Austenite (Isothermal)
Figure 14 is typical micrographs showing the effect
of austenite defhrmation on the progress of ferrite
transformation.Z5) Specimens of an Fe-0.12C-0.04-
Nb-0.04V steel were austenitized at 1 200°C for 30
min, rolled 30 or 50 % in reduction by a single pass
at 840°C (in the unrecrystallized temperature range)
and held at 680°C for 15, 30 and 180 s. The ferrite
transformation is clearly accelerated by deformation
COOLI NG IRATE , K is
Fig. 1 l'erritc grain s i ~ e as a function of cooling rate lor
the specimens of D, = 15 1 pm. (S 15C) Fig. 13. Ferrite grain size as a function of Q-0.2'3Dt4G.
Not Rolled Rolled (30%) Rolled (50%)
(a) Non-deformed, 15 s (b) 30 % rolled, 15 s (c) 50 % rolled, 15 s
(d) Non-deformed, 30 s (e) 30 % rolled, 30 s (f) 50 % rolled, 30 s
(g) Non-defbrmed, 3 min (h) 30 % rolled, 3 min (i) 50 0/6 rolled, 3 min
Fig. 14. Optical micrograph showing the efrect of austenite deformation on the proccss of' ferrite transfbrma-
tion at 680°C in a Fe-O.12C-0.04Nb-0.04V steel.
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( 771 )
ofaustenite. I n the non-deformed specimen austenite
grain boundaries are the predominant nucleation sites
of ferrite, but in the deformed specimens nucleation
occurs not only on austenite grain boundaries but also
within grains. Moreover, the nucleation rate on
grain boundaries is substantially accelerated.
Figure 15 shows various types of nucleation sites of
ferrite observed in deformed specimens.25) Figure
15(a) shows ferrite grains nucleated at austenite grain
boundaries. The ferrite grains grow into both sidcs
of austenite grains, and the prior austenite grain
boundaries disappear once ferritcs are nucleated. Fig-
ure 15(b) shows the ferrite grains nucleated at the
annealing twin boundaries. In contrast to the non-
deformed specimens, the annealing twin boundaries
in the deformed specimens are the preferential nuclc-
ation site of ferrite. The ferrite grains nucleated at
annealing twin boundaries grow mostly into one side,
and the traces of prior annealing twin boundaries
remain after transformation. Figure 15(c) shows fer-
rite grains nucleated intragranularly. These ferrites
were considered to be nucleated on the dislocations at
the cell wall distributed almost uniformly inside the
grains. Figure 15(d) shows the ferrite grains nucle-
ated at decormation bands.
The increase in the ferrite nucleation rate per unit
volume of austenite by deformation is attributed (1)
to the increase in the austenite grain surface by elon-
gation of grains, (2) to the increase in the nucleation
rate per se per unit area of grain surface, and (3) to
the formation of additional nucleation site such as
annealing twin boundaries, deformation bands, etc.
The grain boundary surface area of austenite per
unit volume of a specimen increases by deformation.
A spherical austenite grain (Fig. 16(a)) becomes an
ellipsoid as shown in Fig. 16(b) by applying the roll-
ing with reduction p. The surface area of a grain
with an unit radius before rolling is given as
The surface area of the grain after rolling with reduc-
tion p is given as
S,.,,(p) = St''-* [(q x J: J 1 -(2p-pvsiFzB do.
-1'1-*
l h c ratio of the surface area before to after rolling,
q(=S,.b/SO,.,,), is plotted in Fig. 17 as a function of
rolling reduction p. Since the volume of the sphere
shown in Fig. 16(a) is equal to that of the ellipsoid
shown in Fig. 16(b), the ratio q in Fig. 17 is equal to
that obtaining to grain surface areas per unit volume
before and after rolling. I t is seen that the increase
in the grain surface area per unit volume with the in-
crease in p is quite small when p is smaller than 0.5.
For instance 50 % reduction by rolling increases the
surface area by 25 %. This increase is equivalent to
that obtained by only 20 0/, reduction in austenite
grain size.
The number of ferrite grains nucleated on austenite
grain boundaries is substantially increased by defor-
mation. Figure 1825) shows the ferrite grains nu-
cleated on the austenite grain boundaries: (a) non-
deformed, (b) 30 % rolled, and (c) 50 % rolled,
respectively. From these pictures the acceleration of
ferrite nucleation rate on austenite grain boundaries
by deformation can be estimated. The number of
ferrite grains intersect per 1 mm of austenite grain
(a) (b)
(a) Kcfore rolling (sphere)
(b) After rolling (ellipsoid)
l i g. 16. Tlic shapc change ol' an austcnite grain by the
rolling with reduction p.
Rolled (30V0) 30s Rol led(30%) 15s
(a) W~ ~ c . l t , ~ ~ t i o ~ ~ ;it gr~ii11 I>o~~n(laric~s
(I,)
Nuc.l(.atiun on ; i ~ni ~. nl i ~i g t \ \ . i r ~ I)ou~~cl ; i ri c~~
(c.) S~i cl cnt i on i n d c gr;iinr
((1) Suclc:~tion on clt.IL1.1nntion bantls
Fig. 15.
Opticxl n>ic.rogl.nplis showi~lg lllr \ . ; ~r i o ~~i types 01'
~iucleatiun bites 01' IC3rrite obier\,ccl i l l drll1.111rd
specimens. Rolled(50%) 15s Rolled(30%) 15s
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strain & (=-ln(1-p))
0 -0.5 - 1.0
1 7
--
1.6
--
1. 5
--
1.4
--
1.3
--
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Rolling Reduction p
Fig. 17. The ratio of austenitc grain surfacc arca bcforc
rolling to that of after rolling as a f~~nct i on of roll-
ing rcduction $.
boundaries werc counted as 4 1, 214 and 330 for
0, 30 and 50 rolled specimens, respectively. The
numbers of ferrite grains nucleated per unit area
of austenite grain boundary surface are proportional
to the square of these numbers. Furthermore the
number of ferrite grains nucleated per unit area of
austenite grain surface, n,, is proportional to the
square root of I, as is shown in Eq. (10). Since a is
not much changed by deformation, the ferrite nuclea-
tion rate per unit area of austenite grain boundary
surface is estimated to be increased by 740 ((214/41)4)
and 4 200 ((330/41)4) times faster by 30 and 50 %
rolling, respectively.
As is shown above, the nucleation of ferrite on
austenite grain boundaries is substantially accelerated
by deformation. The mechanism of enhanced nu-
cleation is considered to be as follows. The deformed
austenite grain boundaries may have many ledges (or
steps) shown schematically in Fig. 19(a). If ferrite
nucleates at the corner or such a ledge, as is shown
in Fig. 19(b), the activation energy for nucleation be-
comes B/n times less than that fbr nucleation on a
planar grain boundary (if the surface energy is as-
sumed to be equal for all kinds of interfaces). Thus
if a large number of ledges are produced on grain
boundaries by deformation, considerable increase in
the nucleation rate can be expected. As is shown
in Fig. 15(b) the annealing twin boundaries in
work-hardened austenite also act as the preferential
nucleation site of ferrite. The reason of this can be
considered to be as follows. At the coherent twin
boundaries before deformation a large number of
ledges are produced on the twin boundaries by
deformation. Thus deformed twin boundarics have
Not Rolled
680 'C
3min
Rolled (5O0Io)
680 O C
30s
(a)
Non-deformed, 3 min at G80°C
(b)
30 0/, rolled, 3 s at 680°C
(c)
30 % rolled, 3 s at 680°C
1 18. Optical micrographs showing the efycct of defor-
mation on the number of ferrite formed on auste-
nite grain boundaries.
$.,,.,j- rcrrite
,A-F
(a)
A ledgc on grain boundary
(b)
Ferrite nuclcation at a lcdgc
Fig. 19. Scllematic drawing showing ferrite nucleation at
a ledge on deformed austcnite grain boundaries.
the similar structure with that of austenite grain
boundary surfaces and act as the preferential nu-
cleation site of ferrite.
Similar mechanisms have bcen proposed for the
enhanced nucleation on deformed austenitc grain
boundaries by several researchcrs. Sandberg and
Robertsz7) have suggested that deformation leads to
the formation of grain boundary serrations or bulges,
and these act as nucleation sites. Amin and Pic-
keringZ8) proposcd that deformed austenitc grain
boundaries appear to exhibit greater lattice mismatch,
possibly because of greater lattice distortion and a
higher dislocation density near deformed grain bound-
aries. These would be the predominant nucleation
sites of ferrite and hence accelerate the nucleation.
Deformation structures within austenite grains have
bern known to act as the effective nucleation sites of
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( 773 )
ferrite and play an important role in the ferrite grain
refinement. The deformation structure is generally
called as deformation bands. These regions are char-
acterized by a high density of cells consisting of tangled
dislocations. Dislocations are favor nucleation sites
through its stress field. Consequently ferrite nuclea-
tion appears to occur frequently at the deformation
structures.
2. Growth of Ferrite in Deformed Austenite (Isothermal)
When ferrite grains grow into deformed austenite,
their growth rate would be accelerated by the follow-
ing two factors. One is due to the enhancement of
diffusivity by dislocations and supersaturated vacan-
cies. Another is due to the additional driving force
associated with stored energy. Since carbon, whose
diffusivity controlls the growth rate of ferrite in HSLA
steels, is an interstitial element, the former effect is
considered to be small. The latter [actor is also not
so large estimation by some kinds of calculation (ac-
celeration is less than 10 %).z4) We can find that the
ferrite growth rate is slightly enhanced by the defor-
mation of austenite. The acceleration of growth rate
by deformation is much less than enhancement of nu-
cleation rate for the transformation kinetics.
3. Ferrite Grain Size firmed ,from Dfirmed Austenite
(I~othermal)2~)
For simplicity we assume;
(i)
that austenite grain boundary surfaces are the
nucleation site and the additional nucleation sites
produced by deformation are the deformation bands
and annealing twin boundaries,
(ii)
that the nucleation rates per unit area of de-
formation bands and annealing twin boundaries are
equal to that of the grain boundary surface,
(iii)
that the total area of deformation bands and
annealing twin boundaries per unit volume of auste-
nite is quadratic with respect to
the strain E ( = -In (1 -P)), i.e.,
S,.,i(p)+Sl.l,(p) = A(- In (1 -p))2 ......... (27)
where, A is a constant, and
(iv)
that the ratio JI, (p)/ a(p) can be expressed
as a function of strain e as,
where, Io, a,: the nucleation rate and parabolic rate
constant of growth in the non-de-
formed specimen, respectively
B: a constant.
An exponent of 1.3 came from an experiment for Fig.
18.
As discussed above the ferrite grain size formed
from non-deformed austenite in the case of grain sur-
face nucleation can be expressed by Eq. (1 1). From
the assumptions made for deformed specimen Sg.b in
Eq. (1 1) should be replaced by the effective interfacial
area, S,, which is the sum of the areas ofgrain bound-
ary surface, annealing twin boundary and deforma-
tion bands ( S, ( P) =Sg . b ( p ) +Sd . ~( P) +St . h( P) ) . Fur-
thermore, if both the nucleation and the growth rates
are a function of strain, the ferrite grain size in the
deformed specimen is considered to be expressed as
Thus if d I o / wo and the coefficients A and B are de-
termined from an experiment, the ferrite grain size
formed from deformed austenite can be calculated.
Figure 20 shows an example of such calculation.
Here the calculated ferrite grain size using the com-
monly observed values of JIi/cuo, A and B is plotted
as a function of the rolling reduction, P. From this
figure it is seen that the ferrite grain size formed from
work-hardened austenite decreases drastically with the
increase in a rolling reduction for a small rolling re-
duction and decreases gradually for a large rolling
reduction.
4. Ferrite Grain Refinement by Accelerated Cooling
Accelerated cooling after hot rolling is currently
being realized as a further advanced thermomechani-
cal treatment in hot rolling proce~s.29>3~) This cooling
process is characterized by accelerated cooling in a
7-+a transformation range just after controlled rolling.
I t has been shown that the accelerated cooling refines
the ferrite grain size and thus further improves both
the strength and toughness.
The effect of accelerated cooling on ferrite grain
refinement can be seen in a non-deformed specimen.
Figure 13 and Eq. (24) show the effect of cooling rate
on ferrite grain size in an Fe-0.15C
This dependence of ferrite grain size by cooling
rate means that when a cooling rate becomes 10 times
faster ferrite grain diameter becomes almost half
(0.55).
The principle of grain size refinement by accel-
erated cooling can be understood by considering the
effect of transformation temperature on ferrite grain
size in an isothermal transformation. As mentioned
in the previous section the grain size of isothermally
formed ferrite depends on the ratio of the square root
Da(prn)lnDa True Strain & = -ln(l-p)
1.0 2.0
40
30.-
20-3 0 Austenite Grain Size
10..
2 .o
5-
1.0
0 .I .2 .3 .4 .5 .6 .7 .8
Rolling Reduction, p
Fig. 20. Calculated ferrite grain size formed from work-
hardened austenite as a function of rolling reduc-
tion for various austenite grain sizes.
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[ 7 7 4 ) Transactions ISIJ, Vol. 27, 1987
of nucleation rate to the parabolic rate constant for
various types of nucleation sites. Thus when the
ratio d n a increases with the decrease in the transfor-
mation temperature, the grain size of an isothermally
formed ferrite decreases with the decrease in the
transformation temperature.
The continuous cooling transformation can be con-
sidered as the sum of short time isothermal holdings
at successive temperatures, as described in previous
section and derived two equations of (21) and (22)
which show n, and D,, respectively.
As a whole, austenite deformation results in a large
increase in the ratio of the nucleation rate to the
parabolic rate constant and leads to ferrite grain re-
finement. The accelerated cooling further refines a
ferrite grain size.
V. Structures and Properties of Martensite
Formed f rom Work-hardened Austenite
I . Morfhology of Microstructure Composed of Lath Mar-
tensite Formed from Work-hardened Austenite
Among various types of ferrous martensite (such as
lath, lenticular, etc.) the lath martensite is the most
important one because most of the commercial heat-
treatable steels produce lath martensite. Lath mar-
tensite structure is characterized by packets and blocks
within a original austenite grains as shown schemati-
cally in Fig. Zl.31) It is known that the basic micro-
structural unit for controlling mechanical properties
especially, toughness of lath martensitic steel is size of
packets or bl o~ks, ~2-3~) and thus the refinement of
packets or blocks improves the mechanical properties
of lath martensitic structure. Therefore, we examined
the change in lath martensite morphology with the
amount of deformation of austenite using an 18 Ni
maraging steel (18.3 % Ni, 9.0 % Co, 5.0 % Mo, 0.7
% Ti, 0.015 % C) and Nb bearing low carbon steel
(0.12 % C, 0.038 % Nb, 0.039 % V).
An example of results in 18 Ni maraging steel is
shown in Fig. 22.35) In this case, specimens were
austenitized at 1 523 K for 120 s in Ar gas atmosphere
(austenite grain size of 200 pm was obtained by this
treatment) and cooled to 773 K (above M d tempera-
ture) and deformed in tension to various strains at
773 K at strain rate of 3 x 10-2/s and then air cooled
to room temperature to produce lath martensite. It
appears from Fig. 2233) that the number of packets in
an austenite grain markedly decreases and hence the
packet size becomes large with an increase in the
amount of deformation of austenite. The block be-
comes narrower and finely segmented, and the block
boundaries become heavily waved with an increase in
the amount of ausforming. Figure 23 shows the
change in the mean packet size and block width of
lath martensite in 18 Ni maraging steel with the
amount of ausforming. These results indicate that
the morphology of ausformed lath martensite is char-
acterized by large packet size and less-developed
blocks. And also it is characteristic that the block
boundaries are waved in the case of ausformed mar-
tensite. Similar tendency was observed in low carbon
Nb steel (HSLA steel) as shown in Fig. 24, in which
the specimen was rolled at 1 123 K by 50 % after
austenitizing at 1 573 K for 1.8 ks and then water
quenched to produce lath martensite. These micro-
structural characteristics might arise from the pre-
ferential formation of lath martensites with the same
habit plane along the most active slip plane (one of
four (11 11, planes) which is macroscopically bent by
heavy deformation.
As shown above, the packet size of ausformed mar-
tensite is large compared with that of conventionally
quenched lath martensite. I t was observed that the
ausformed lath martensites form along the curved
{111}, planes as shown in Fig. 22(f)35) and Fig. 24
(b).") This indicates that the crystal planes of aus-
tenite (and hence, of martensite) are bent. I n such
a situation, there would be a possibility that the
propagation of cleavage crack is suppressed since the
plane of cleavage fracture ({001],,) is heavily waved.
This might be one reason for some improvements in
toughness by ausforming in spite of the coarsening of
packet size.
2. Mechanical Proferties of Ausformed Martensite
In order to account for the good ductility of aus-
formed steels, the relation between the ductility of de-
formed austenite and the ductility of ausformed mar-
tensite was studied using an Fe-25.4XNi-0.38XC
alloy (Ms=236 K).37) I n this experiment, specimens
were solution treated at 1 423 K for 10.8 ks. Since
the M s temperature of this alloy is below room tem-
Fig. 2 1. Schematic illustration showing the morpholog-
I
0.2% Carbon Steel
I
ical characteristics of lath martensite structure
l8Ni Maraging Steel
in 0.2 0/, C steel and 18 % Ni maraging steel.
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( 775 )
( a ) ( c ) :
Packed structure (electrirally etched with CrO, 10 g+H, O 90 cc)
( d ) ) :
Block structure (chemically etched with FeCI, 10 g+HCl 30 cc+H, O 120 cc)
Fig. 22. Optical micrographs showing the change in packed or block structure of lath martensite with
amount of deformation oT austenite (ausformed by tennion at 773 K) in 18Ni maraging steel.
1
0 0.1 0.2 0.3 0.4 0.5 0.6
True Strain
Fig. 23. Change in the packet size and block width of lath
martensite with the amount of deformation of
austenite (ausformed at 773 K) in 18Ni maraging
steel. D, = 200 pm.
perature, the solution treated specimen was austenite
single phase at room temperature. These specimens
were deformed at 473 K by rolling to various amounts
of reduction. The rolling temperature of 473 K was
applied in order to avoid the formation or strain-
induced martensite during deformation. Some of
specimens of deformed austenite were subzero cooled
into liquid nitrogen to produce the ausformed mar-
tensite. Tensile properties were measured in both
specimens of deformed austenite and ausformed mar-
tensite with an Instron-type tensile machine at 353 K
(a)
1 573 K for 1.8 ks -+ W. Q.
(b)
1 573 K for 1.8 ks --t 50 % rolled at 1 123 K
-t w.9_.
Fig. 24. Optical micrographs of non-ausformed (a) and
ausformed (b) lath martensite in Nb steel.
Etchant: 2 % nital.
which is above Md temperature.
Figure 25 shows the results of tensile strength of the
deformed austenite and the ausformed martensite.
Both of tensile strengths of austenite and martensite
are increased with an increase in the amount of
prior-deformation of austenite. Figure 26 shows the
relation between the elongation and the amount of
prior-deformation of austenite. In the case of de-
formed austenite, the elongation is markedly decreased
(from 60 to 3 %) with an increase in the amount of
prior-derormation. On the other hand, it is charac-
teristic that the elongation of ausformed martensite is
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Transactions ISIJ, Vol. 27, 1987
Test temperature: 353 K
P, T: Parallel and transverse specimens against
rolling direction, respectively
S: Subzero cooling to 77 K, namely speci-
mens are of martensite
Fig. 25. Relation between tensile strength and the amount
of prior-deformation of austenite at 473 K in
Fe-25Ni-0.38C alloy.
hardly effected by the amount of ausforming and is
almost same as the elongation of non-ausformed mar-
tensite. The ausformed martensite exhibits almost
constant elongation of about 8- 10 %, irrespective of
the amount of ausforming. Therefore, the elongation
of deformed austenite becomes smaller than that of
ausformed martensite, when the amount of deforma-
tion (ausforming) is more than about 30 % in the
case of the present alloy. I t must be emphasized that
the heavily deformed austenite is rather enhanced in
both strength and ductility by martensitic transforma-
tion.
These results indicates that the dislocations in
austenite produced by deformation are inherited and
that the stress concentrated region at the obstacles in
austenite produced by heavy deformation are healed
by the martensitic transformation itself. As a reason
for the healing effect, it can be considered that the
stress concentration in austenite may be released by
the formation of preferential variants of martensite at
the stress-concentrated areas.
3. Effect of Ausforming Temperatures on the Increase of
Strength ff Ausformed Martensite
I n the most published papers, the strength of aus-
0 15 30 L5 60
Pre-deformation ( % )
Test temperature: 353 K
Fig. 26. Relation between elongation and the amount of
prior-deformation of austenite at 473 K in Fe-
25Ni-0.38C alloy.
formed martensite has been studied mainly by func-
tions of the amount of deformation and the defor-
mation temperature below Al . And it is generally
believed that the increase in the strength of ausformed
martensite is closely related to the amount of work-
hardening of austenite. However, few attempts have
been made to relate the strength of ausformed mar-
tensite to the flow stress of austenite during ausform-
ing at elevated temperatures.
I n order to make clear this point, the experiment
was carried out using austenitic steels (a high Mn
steel : 13.9 % Mn, 0.68 % C) and Fe-high Ni alloy
(32.4 % Ni 0.005 % C), and martensitic steels (SNC
815: 3.0 % Ni, 0.8 % Cr, 0.16 % C).38) Ausforming
was performed with a tensile machine at various tem-
peratures between 773 and 1 173 K at strain rate
of 1 . 7 ~ 10-21s. After deformation, specimens were
rapidly quenched by water spray. These ausformed
specimens were tensile tested at room temperature at
strain rate of 1 . 7 ~ 10-3/s to measure the yield stress of
deformed austenite (austenitic steels) and ausformed
martensite (martensitic steels) at room temperature.
Figure 27 shows the relation between the increase
in 0.2 % proof stress at room temperature (Aa;.,) of
ausformed austenite and the amount of work-harden-
ing (Aar) of austenite by ausforming at elevated tem-
peratures in austenitic steels. It appears that the
yield stress increase of austenite (Aa;.,) at room tem-
perature is linearly proportional to the amount of
work-hardening of austenite (Aur) by ausforming in
both steels, and all data lie on the same straight line,
irrespective of ausforming conditions such as defor-
mation temperature and the amount of strain. This
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(777)
result indicates that the strength of ausformed austen-
ite at room temperature is uniquely determined only
by the amount of work-hardening by ausforming.
This probably suggests that the strengths of austenite
at both of high and room temperatures are mainly
determined by the dislocation density.
Figure 28 shows the relation between the increase
of 0.2 % proof stress of ausformed martensite (Au;:~)
(i.e., the difference of 0.2 % proof stress at room tem-
perature between ausformed martensite and conven-
tionally quenched martensite) and the amount of
work-hardening (Aar) in austenite at elevated tem-
perature in SNC 815 steel. It is characteristic that
the obtained data lie on the different curves by the
ausforming temperature. It should be emphasized
that the d a f , is not determined only by the Aar, but
functions of both Aar and ausforming temperature.
Even at the same Aar, the effect of ausforming on the
strengthening of martensite is different with the de-
at H.T.
E
Fig. 27. Relation between the increase in 0.2 O//o proof
stress at room temperature of ausformed austenite
(do:,) and the amount of work-hardening of
austenite (Aor) by ausforming in austenitic steels.
formation temperature, i.e., do;:, is increased with an
increase in deformation temperature. Furthermore,
when the ausforming temperature is fixed, the con-
tribution of A 0 7 on the An;:, is small at smaller Aur
range and becomes large at larger Aar range. Same
tendency was also observed in SKD 61 steel. These
results strongly suggest that, in addition to the dislo-
cation density in austenite, the dislocation configu-
ration in austenite is also an important factor for
increase in strength of ausformed martensite.
Figure 29 shows the examples of transmission elec-
tron micrographs of austenite in a high Mn austenitic
steel deformed to the same amount of work-hardening
(Aor= I0 kg/mm2) at different temperatures. As can
be seen, the total dislocation density seems to be
almost same, but the dislocation configuration is dif-
ferent from each other. With increase in the defor-
mation temperature, the dislocation configuration is
changed from uniformly distributed pile-up to disloca-
tion cells. I n this austenitic steel, despite the dif-
ference of dislocation configuration the 0.2 % proof
Deformat ion temperature:
30
- A -993K
-1023K
25. o -1073K
L1
E
E 0
b 2 0 -
Y 0
e
rT 15-
C
0
- N
0
Q 0
5 .
0 5 10 15 20
bar at H.T. kg.rnrn-=
Fig. 28. Relation between the increase in 0.2 % proof
stress of ausformed martensite (dot,;) and the
amount of work-hardening of austenite (do?) by
ausforming in SNC 813 steel (3Ni-0.8Cr-0.16C).
Fig. 29. Transmission electron micrographs of austenite deformed to the same amount of work-hardening of
austenite ( Au~= 10 kg/mm2) at strain rate of 1.7 x 10-2/s at (a) 1 073 K, (b) 1 023 K and (c) 873 K,
respectively, in Fe-14Mn-0.7C austenitic steel.
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Transactions ISIJ, Vol. 27, 1987
stress of austenite at room temperature is the same as
shown in Fig. 27, because the Aar is the same. How-
ever, as shown in Fig. 28, in the case of ausformed
martensite, Aa$, is increased as the ausforming tem-
perature is raised even at the same Aor. Therefore,
it can be considered that the dislocation cell structure
in prior austenite is very effective in strengthening of
ausformed martensite through the martensitic trans-
formation, and pile-up or uniformly distributed dis-
locations in prior austenite have little effect on
strengthening of ausformed martensite.
VI. Hardenability of Work-hardened Austenite
and Recrystallized Austenite
As described in the former section, the work-hard-
ened austenite can transform easily by diffusional
process, because the rate of nucleation of ferrite is
high. It means that the hardenability of steel is de-
creased with work-hardening of the austenite.
A bearing steel (SUJ2: 1.33 % Cr, 0.9 % C) with
spheroidized carbide particles was austenitized at
850°C at which the steel was in two phase region of
y and carbide, and deformed by compression of 60 %
(s=3x 10°/s), and then immediately or after holding
in some intervals of time (At) at the same temperature
as the deformation quenched into water. The hard-
ness at the center portion of SUJ2 specimen at room
temperature after quenching changed with holding
time (At) as shown in Fig. 30.
The austenite of SUJ2 with spheroidized carbide
particles can dynamically recrystallized easier than
without carbide particles. The work-hardened aus-
tenite of SUJ2 has poor hardenability and becomes its
hardenability recover to usual SUJ2 with holding
time (At) during the static recrystallization is progress-
ing as shown in Fig. 30.
Ausforming is quenching method of work-hardened
austenite. Such an austenite has poor hardenability.
The steel for ausforming should have high harden-
ability by including several alloying elements of Ni,
Cr, Mo, etc.
For direct quenching it seems that the austenite is
deformed and recrystallized and then quenched. In
this case, we can not expect to increase strength and
toughness of martensite as ausforming does.
I I I I W.Q.
6001 100 1
200 300 400
~t Hold~ng Time ( 5 )
Fig. 30. Change in hardness of water-quenched specimen
with holding time after deformation at 850°C in
SU.J2.
VII. Conclusion
I have explained the abstract of kinetics, structure
and mechanical properties of transformation products
of ferrite and martensite formed from work-hardened
austenite. Because of too much contents, I am afraid
that it would be difficult to understand.
Thank you very much for your kind attention.
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3.5) I. Tamura, K. Tsuzaki and T. Maki: Proc. of Int.
Conf. Martensitic Transformation (ICOMAT-82), ed. by
L. Delaey et al., Les Edition de Physique, Paris, Leuven,
(1982), c4-551.
36)
I. Tamura, T. Maki and H. T. Yui: to be published.
37)
Y. Tomota, K. Tanabe, K. Kuroki and I. Tamura:
J.
J p n Inst. Met., 41 (1977), 313.
38)
C. K. Yao, S. Y. Gao, T. Maki and I. Tamura: Proc.
3rd Int. Cong. Heat Treatment of Materials, ed. by T.
Bell, Metals Soc., London, Shanghai, (1983), 5-80.
Special Lecture
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Journal of Applied Sciences Research, 2(8): 484-485, 2006
© 2006, INSInet Publication
Corresponding Author:
2
O.E. Olorunniwo, Department of Material Sciences and Engineering,
Obafemi Awolowo University, Ile-ife. Osun state, nigeria
484
Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment
1
J.A. Omotoyinbo,
2
O.E. Olorunniwo,
2
O. Ogundare and
2
O.O. Oluwole
1
Federal University of Technology, Akure. Nigeria.
2
Obafemi Awolowo University, Ile-Ife. Nigeria.
Abstract: Micro-alloyed steels produced by controlled rolling are of the most attractive propositions in many
engineering applications because of their relative low cost, moderate strength and very good toughness when
compared withas-cast alloy steel.. This research work has shownthe possible substitution of cheaper, low-alloy
steel for the highalloy steel for the same application. The effect of HTMT onthe mechanical properties of low
alloy steel was investigated.
Key words: Strengthening. High Temperature Themomechanical Treatment (HTMT), micro alloyed,
controlled rolling.
INTRODUCTION
Steels are weaker than they should be theoretically
because of dislocations and the ease with which these
dislocations moveunder applied shear stress
[4]
. Therefore,
the primary aim of strengthening is to retard the
dislocationmovements. However, complete barrier canbe
dangerous because pile-up of dislocations can lead to a
catastrophic crack
[2]
.
Strength in steels arises from several phenomenon
including solid solution strengthening, dispersion
strengthening and ferrite grain refinement which usually
contribute collectively to the observed mechanical
properties such as ductility, strength,etc. Alloying
elements’ presence provides greater control over
microstructure and consequent benefit in mechanical
properties.
Therefore, to produce steels with improved
strength-to-ductility ratio, a combined use of mechanical
working and heat treatment is employed as
strengthening mechanism
[8]
, resulting in structural steels
withimproved weldability, cleannessand inclusionshape
control
[9]
.
This paper seeks to investigate and establish the
possible benefits derived from strengthening of alloy
steels by HTMT. This includes improved mechanical
properties, substant ial energy savings (through
elimination of subsequent normalizing treatment) and
possible substitution of cheaper, low alloy steel for high
alloyed steel for the same application under the same
conditions.
Experimental procedure: The chemical composition of
low alloy steel as-cast specimens (AISI-SAE 1037),
presented in table 1, was obtained from the Universal
Steels Limited, Lagos, Nigeria. All mechanical tests
(tensile, hardness, impact) were carried out according to
the A 296 ASTM requirement.
MATERIALS AND METHODS
Tensile test samples: To prepare the tensile test
specimen, the hot-rolled samples which were initially of
round shape were prepared as follows. The 10mm
diameter rod was held tightly in position on the bench
vice where it was cut into lengths of 5mmach with he aid
of hack saw. Each of the samples was then mounted and
turned consecutivelyon the lathe machineinto cylindrical
shape. The vernier caliper was used to take the accurate
measurement. For reproducibility of results, four samples
were prepared for the 10mm diameter rod. This process
was repeated for the 12mm and 16mmdiameter rod, one
after the other.
The impact test samples: They were prepared by
notching to 4mm depth at 45
0
with the aid of the lathe
machine. Four samples were prepared each for 10mm,
12mm and 16mm diameter rod as well as for the as-cast
sample to be used in izod impact test.
The hardness test sample-This sample is obtained by
grindingthe surface with emery paper. Then, withthe aid
of hacksaw and lathe machine, cut into 25mm x 25mm x
25mmsquare cube for Rockwell test. Four samples were
prepared for 12mm and 16m diameter samples.
Microstructural test: The specimens were ground in
successionwith220,320, 400, 600frit emerypaper. Then,
they were polished until mirror-like surfaces was
obtained. The surface was etched withNital solution and
examined under the microscope. For reproducibility of
results, four samples were prepared for 10mm, 12mmand
16mm samples.
RESULTS AND DISCUSSIONS
From the result, it has been shown that the rolled
(HTMT) samples possess both the yield strength and the
Menu Back
J. Appl. Sci. Res., 2(8): 484-485, 2006
485
1 2 3 4
97.99%
Deformation
98.87%
Deformation
92.22%
Deformation
AS.CAST
60
50
40
30
20
10
0
B
r
i
n
e
l
l
h
a
r
d
n
e
s
s
v
a
l
u
e
s
60
50
40
30
20
10
0
1 2 3 4
AS.CAST
97.99%
Deformation
98.87%
Deformation
99.22%
Deformation
I
m
p
a
c
t
v
a
l
u
e
s
(
j
o
u
l
e
s
)
`% red. Fracture UTS Yield strength Hardness Impact
Sample % Elongation in area strength N/mm
2
N/mm
2
N/mm
2
HRC (J)
10mm diam as- rolled 1.80 51.41 668.11 688.78 255.10 47.58 48.15
-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
12mm diam. As –rolled 4.63 56.55 367.36 377.55 239.8 41.4 45.57
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
16mm diam as-rolled 7.81 61.26 213.64 221.94 147.96 37.45 41.40
--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
As-cast 0.80 3.60 171.94 - - 55.78 11.25
Table 1: The low alloy steel specimens used have the following
composition in weight percent as below.
C 0.368 Sn 0.014
Si 0.226 Al 0.003
S 0.33 Zn 0.003
P 0.039 Mo 0.021
Mn 0/688 Cu 0.227
Ni 0.177 As 0.014
Cr 0.119 Co 0.013
V 0.002 Pb 0.001
W 0.003 Fe 98.055
Fig. 1: Average hardness values.
Fig. 2: Impact values
Ultimate Tensile Strength while the as-cast samples do
not. Reasons that could be adduced to these are that,
during the HTMT, the as-cast sample has its defective
structure homogenized, blowholes and gas pores welded
shut and atomic segregation reducedand internal stresses
relieved
[3]
. These, coupled with hot plastic deformation
as well as the presence of alloying elements (carbide
formers such as nickel, titanium, etc), inhibiting
dislocation movement, to effect strengthening with
respect to Ultimate Tensile Strength (UTS) and yield
stress
[2,9]
.
Also, the as rolled (HTMT) samples are much more
ductile than the as cast samples for the same reason cited
above
[6]
. Conversely, the as-cast samples are harder than
the as rolled due to the presence of inclusions, residual
internal stress, residual coring and non-uniformity during
solidification, which are virtually elimination by
HTMT
[1,8]
.
Conclusion: The application of HTMTon low alloysteel
has led to the reductionin hardnesswhile the strength and
toughnessincrease considerably, compared to the as-cast
samples. Hence, for applications that require adequate
me chani cal pr oper t i es, hi gh t emp er at ur e
themomechanically treated low alloy steel should be
employed
REFERENCES
1. Adeyeye Oluseyi, 1996. Influence of thermo
mechanical working on the strengthening of
Aluminum alloys, Unpublished B.Sc. Thesis,
Metallurgical and Material Engineering department,
Federal University of Technology Akure, Nigeria,
1998
2. Benjamin, W.N., B.D. Alan, and A.W. Richard,
1989. Modern manufacturing process Engineering
McGrawHill, NewYork, pp: .32-33, 61-62 , 77-114.
3. Bolton, 1988. Production Technology-Processes,
Materials and planning Heinemann London pp:
174-185.
4. Dieter, G.E. 1988 Mechanical metallurgy McGraw
Hill, London, pp: 309-312.
5. Degarmo, E.P., J.T. Black and A.K. Ronald, 1993.
Materials and processes in manufacturing, 7th Edn.
Macmillan, London, pp: 222-223.
6. Higgins, R.A., 1993. Engineering Metallurgy part 1:
Applied Physical Metallurgy’ 6th Ed. 124: 219-233,
285-330.
7. Llewellyn, D.T., 1992. Steels: metallurgy and
application’ 1st Edn., Butterworth Heinemann,
oxford, pp: 64-77.
8. Rajan, T.V, C.P. Sharma and A. Sharma, 1988. Heat
treatment-principle and techniques, McGraw Hill,
India, pp: 175-181.
9. Novikov, L., 1978. Theory of Heat treatment of
metals,’ 1st Edn. Moscow, pp: 105-106, 418-425.
10. Honeycombe, RWK, 1981. Microstructure and
properties’ 1st Ed., Edward Arnold, London, pp:
167-185.
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Ion-nitriding of Maraging steel (250 Grade) for
Aeronautical application


Kishora Shetty
1,2
, Subodh Kumar
3
and P. Raghothama Rao
2


2
Regional Centre for Military Airworthiness (Foundry and Forge), CEMILAC, DRDO,
Bangalore-560 037, India.

3
Department of Materials Engineering, Indian Institute of Science, Bangalore-560 012, India.

E-mail: kishora_shetty@yahoo.com

Abstract. Ion nitriding is one of the surface modification processes to obtain better wear
resistance of the component. Maraging steel (250 Grade) is used to manufacture a critical
component in the control surface of a combat aircraft. This part requires high strength and
good wear resistance. Maraging steels belong to a new class of high strength steels with the
combination of strength and toughness that are among the highest attainable in general
engineering alloys. Good wear resistance is achieved by ion-nitriding

(also called as plasma
nitriding or glow discharge nitriding) process of case nitriding. Ion-nitriding is a method of
surface hardening using glow discharge technology to introduce nascent (elemental) nitrogen
to the surface of a metal part for subsequent diffusion into the material. In the present
investigation, ion-nitriding of Maraging steel (250 grade) is carried out at 450
0
C and its effect
on microstructure and various properties is discussed.


1. Introduction
Surface Engineering means ‘engineering the surface’ of a material or components to impart
surface properties, which are different from the bulk of base material [1]. The purpose may be to
reduce wear, minimize corrosion, increase fatigue resistance, reduce frictional energy losses,
provide a diffusion barrier, provide thermal or electrical insulation, exclude certain wave lengths
of radiation, promote radiation, electronic interactions, or simply improve the aesthetic
appearance of the surface. Surface engineering processes, which give required properties at
surfaces include flame hardening, induction hardening, laser hardening, carburizing, nitriding,
cyaniding, plasma nitriding, ion implantation, weld overlay, roll cladding, thermal spraying,
plasma spraying, ion plating, CVD, PVD etc. Nitriding is a process for case hardening of alloy
steel in an atmosphere consisting of a mixture of ammonia gas and dissociated ammonia [2]. In
ion-nitriding (also called as Plasma nitriding or Glow discharge nitriding) method glow discharge
technology is used to introduce nascent (elemental) nitrogen to the surface of a metal part for
subsequent diffusion into the material [3-5].

1
To whom any correspondence should be addressed
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The plasma assisted surface modification techniques offer a great flexibility and are capable
of tailoring desirable chemical and structural surface properties independent of the bulk properties
[3]. It has other advantages like nil or very thin white layer after nitriding and there is no
machining or grinding involved for complex parts after the process. The hardened surface layers
become an integral part of the base material without any significant reduction in properties of
base material. It is also known to provide the modified surface without dimensional change or
distortion of the component. Ion-nitriding provides better control of case chemistry and
uniformity [3,6,7]. This method is one of the most effective techniques for increasing wear
resistance, fatigue strength, surface hardness and corrosion resistance of industrial components
[8]. In this process, vacuum environment and high voltage electrical energy is used to form
plasma through which nitrogen ions are accelerated to impinge on work piece. The ion
bombardment heats the work piece and cleans the surface as the active nitrogen diffuses through
it [3,9].
Maraging steels belong to a new class of high strength steels with the combination of strength
and toughness that are among the highest attainable in general engineering alloys [10]. These
steels differ from conventional steels in that they are hardened by a metallurgical reaction that
does not involve carbon. These steels contain very low carbon (<0.03%) and are strengthened by
the precipitation of intermetallic compounds at temperature about 480
0
C [11-13]. The term
maraging is derived from martensite age hardening and denotes the age hardening of a low
carbon, iron – nickel lath martensite matrix [12,14]. Different maraging steels are designed to
provide specific levels of yield strength from 1030 to 2420 MPa (150 to 350 ksi). These steels
typically have very high nickel, cobalt and molybdenum and very low carbon content. Carbon is
treated as an impurity in these steels and is kept as low as commercially feasible (<0.03%) in
order to minimize the formation of Titanium carbide (TiC), which can adversely affect strength,
ductility and toughness [11,12]. Nominal composition of 250 Grade is Fe-18Ni-8.5Co-5Mo-
0.4Ti-0.1Al [10].
Good wear resistance of Maraging steel can be achieved by ion-nitriding process of case
nitriding. In conventional gas nitriding process, the nitriding temperature is 500
0
C – 550
0
C
[2,15], which is above the ageing temperature of maraging steel. Hence ion-nitriding of Maraging
steel (250 grade) at a temperature lower than the aging temperature has been carried out in the
present investigation. Microstructure of the ion-nitrided specimens was examined and properties
like tensile, low cycle fatigue, hardness, case depth and corrosion by salt spray test were
evaluated. These tests were also carried out on un-nitrided specimens for comparison.

2. Experimental
Figure 1 shows a simplified schematic and figure 2 shows the actual ion-nitriding installation.
The work load is supported on a hearth plate inside a double walled, water cooled vacuum
chamber, connected to vacuum pumps and gas supply. The chamber is evacuated to a pressure of
about 2.5 X 10
-2
mbar, a pressure low enough for the background level of oxygen to be within
acceptable limits (less than 50 ppm), then filled with a low pressure mixture of nitrogen and
hydrogen. The use of auxiliary A.C. heaters to heat the cathode to 250 °C is desirable to minimize
cycle time. It can also help provide better temperature uniformity of the part in ion-nitriding
treatment. The discharge is ignited using a D.C. power supply, and pressure and temperature are
raised to the desired operating values by controlling gas flow and pressure, applied voltage and
current. The discharge can be monitored by meters and viewed through inspection windows. The
work is cathode and the vessel is anode. The furnace is electrically grounded, cool to the touch,
and quiet in operation. Maraging steel (250 grade) specimens were prepared from solutionised
material and then aged at 450
0
C for 3 hrs. These aged specimens were ion-nitrided in the
nitriding furnace under the vacuum. Plasma is obtained by passing the gas mixture of H
2
and N
2

gases in the ratio 3:1 into the chamber and maintaining the pressure of 5 mbar. Ion-nitriding is
carried out at 450
0
C for 10 h.

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Figure. 1. Schematic arrangement of an ion-
nitriding system [7].
Figure. 2. Ion-nitriding installation.


3. Results
3.1 Chemical Composition
The chemical analysis of the Maraging steel (250 grade) was carried out using Optical emission
spectroscopy to confirm the material specification. The values obtained are given in Table 1.

Table 1. Chemical composition of the alloy (wt.%).

Element C Ni Mo Co Ti Al S P Fe
Composition 0.01 17.29 4.89 7.90 0.41 0.14 0.005 0.006 Balance

3.2 Visual Check
Ion-nitrided samples were checked for any visible defects and discoloration and no defects were
observed.

3.3 Microstuctural studies
The samples for Metallography were prepared from both ion-nitrided and un-nitrided samples.
Microstructural studies were carried out using both optical microscope and scanning electron
microscope (SEM). Optical micrographs of un-nitrided specimen is shown in figure 3 and that of
ion-nitrided specimen is shown in figure 4. Etchant used here is Ferric Chloride. SEM studies
were carried out by etching the specimens using Ferric Chloride. The microphotographs obtained
from un-nitrided and ion-nitrided samples are shown in figures 5 and 6 respectively.





Figure 3. Optical micrograph of un-
nitrided sample showing martensite
structure.
Figure 4. Optical micrograph of ion-nitrided
sample showing martensite structure at the
core and nitrided layer at the case.
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Figure 5. SEM micrograph of un-nitrided
sample.


Figure 6. SEM micrograph of ion-nitrided
sample.

3.4 Hardness and Case depth measurement
Hardness was measured for both un-nitrided and ion-nitrided samples using Vickers Hardness
Tester. The hardness values obtained on un nitrided specimen is 616 VPN where as for ion-
nitrided specimen it is 900 VPN.
Case depth was determined by hardness measurements. Hardness values are listed in Table
2. Figure 7 shows the variation of hardness with depth from the surface. Case depth here is taken
as distance from the surface to which hardness is 100 VPN more than the core hardness. From the
graph the case depth estimated is 93 µm.


Table 2. Hardness and corresponding distance from the surface.

Distance from the edge (µm) Hardness (VPN)
50 797
75 761
100 702
125 626
150 623
175 623
200 623
Core 616













Figure 7. Graph of case depth vs hardness

3.5 Salt spray test
Salt spray test was carried out on both un-nitrided and ion-nitrided specimens for 144 hrs at 5 %
NaCl solution in a Salt Spray Test chamber. Figure 8 shows the photograph of samples
500
550
600
650
700
750
800
850
0 25 50 75 100 125 150 175 200 225
Depth from the surface (micrometer)
H
a
r
d
n
e
s
s

(
V
P
N
)

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before and after the salt spray test. Corrosion started in un-nitrided specimen after 48 h of
exposure, whereas no corrosion was noticed in ion-nitrided specimen.



(a)



(b)
1 - Ion nitrided 2 - Un nitrided


Figure 8. (a). Photograph of the samples (a) before the salt spray test and (b) after the salt
spray test.

3.6 Tensile Properties
Tensile properties – Ultimate tensile strength (UTS), 0.2 % Proof stress (0.2 % PS), %
Elongation (% El.) and % Reduction in Area (% RA) were measured using TIRA Test 2820S
Universal Testing Machine (UTM). The results obtained are presented in Table 3.


Table 3. Tensile properties.

Property UTS (MPa) 0.2% PS (MPa) % El. % RA
Sample 1 1694 1606 9.32 60
Sample 2 1696 1619 8.84 56 Un nitrided
Sample 3 1702 1622 9.23 55
Sample 1 1847 1757 5.66 25
Sample 2 1864 1810 6.24 28 Ion nitrided
Sample 3 1877 1813 6.70 30

3.7 Impact Strength
Impact strength was measured on Charpy ‘U’ notch specimens using FIE make Charpy Impact
Testing machine. The values obtained are given in Table 4.

Table 4. Impact strength (Joules).

Sample 1 Sample 2 Sample 3
Un nitrided 21 22 22
Ion nitrided 17 19 19

3.8 Low Cycle Fatigue
Low cycle fatigue testing was carried out on smooth specimens in Zwick Roell UTM with
applied stress of 1172 MPa and with stress ratio (R) of -1. The values obtained are presented in
Table 5.

Table 5. Low cycle fatigue properties (No. of cycles to failure)

Sample 1 Sample 2 Sample 3
Un nitrided 3755 3287 5220
Ion nitrided 5500 14400 11200
1
2
1
2
1
2
1
2
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4. Discussion
Chemical composition analysed conforms to the Maraging steel 250 grade.
Both Optical microscopy and SEM examination confirm that no change in core
microstructure of the material after ion-nitriding occurs.
The ion-nitrided specimens exhibit higher surface hardness and good case depth than the un-
nitrided specimens. The introduction of nitrogen to the surface of Maraging steel by ion nitriding
process improves the wear properties by increasing the hardness.
Salt spray test results show that there is an improvement in corrosion resistance after
nitriding. This is due to the formation of an anodic layer after nitriding.
The ion-nitrided samples show higher UTS and 0.2 % PS values than the un-nitrided ones,
whereas % El and % RA are less for ion-nitrided samples compared to the un nitrided samples.
This can be attributed to the surface layer getting hardened because of ion-nitriding. Impact
strength of ion-nitrided samples is lower compared to un-nitrided samples. This is again due to
the surface layer getting hardened because of ion nitriding.
The number of cycles to failure in low cycle fatigue test also increase on ion-nitriding. The
introduction of nitrogen to surface layers increases the fatigue properties of the maraging steel by
introducing the residual compressive stresses.

5. Conclusions
From this ion nitriding study of Maraging steel (250 grade), the following conclusions can be
drawn.
Case depth obtained is sufficient for the design requirement.
Ion-nitriding improves the surface hardness of Maraging steel 250 grade.
An improvement in UTS, 0.2 % PS and LCF properties is observed on ion-nitriding. The %
El, % RA and impact strength decrease but they satisfy the design requirements.
No change in microstructure observed after ion-nitriding.
Ion-nitriding of 250 Grade appears to be suitable for parts which are subjected to constant
wear.

Acknowledgements
The authors thank Mr. B. S Vedaprakash, Group Director (Propulsion), and Mr. K. Tamilmani,
Chief Executive (Airworthiness), CEMILAC for their support.

References
[1] Kumar B, Upadhyay N C 2005 IIM Metal News 8 5
[2] Sidney Avner H 1997 Introduction to Physical Metallurgy 2
nd
Edition 383
[3] Spalvins T Ion Nitriding Conference proceedings ASM International 1
[4] Moller W, Parascandola S, Telbizova T, Gunzel R and Richter E 2001 Surface & Coatings
Technology 136 73
[5] ASM Handbook 1996 Vol. 5 411
[6] Bernd Edenhofer 1976 Metal Progress 181
[7] EPRI Centre for Materials Fabrication Ohio 1994 Ion nitriding 2
[8] Ahangarani Sh., Mahboubi F and Sabour A. R 2006 Vacuum 80 – Surface Engineering, Surface
Instrumentation & Vacuum Technology 1032
[9] Pavel Novak, Dalibor Vojtech and Jan Serak 2006 Surface & Coatings Technology 200 5229
[10] Gupta B, 1996 Aerospace Materials II 695
[11] ASM Handbook 1991Vol. 4 219
[12] ASM Handbook 1990 Vol. 1 793
[13] INCO Databook, 1976 351
[14] Morito S, X-Huang, Furuhara T, Maki T and Hansen N 2006 Acta Materialia 54 5323
[15] David Pye 2005 Practical Nitriding and Ferritic Nitrocarbourizing ASM International 71
IVC-17/ICSS-13 and ICN+T2007 IOP Publishing
Journal of Physics: Conference Series 100 (2008) 062013 doi:10.1088/1742-6596/100/6/062013
6
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Bull. Mater. Sci., Vol. 29, No. 1, February 2006, pp. 59–66. © Indian Academy of Sciences.
59
Microstructures and properties of low-alloy fire resistant steel
BIMAL KUMAR PANIGRAHI
R&D Centre for Iron and Steel, Steel Authority of India Limited, Ranchi 834 002, India
MS received 10 June 2004; revised 2 November 2005
Abstract. Microstructures and properties of weldable quality low-alloy fire resistant structural steels (YS:
287–415 MPa) and TMT rebar (YS: 624 MPa) have been investigated. The study showed that it is possible to obtain
two-thirds of room temperature yield stress at 600° °C with 0⋅ ⋅20–0⋅ ⋅25% Mo and 0⋅ ⋅30–0⋅ ⋅55% Cr in low carbon
hot rolled structural steel. Microalloying the Cr–Mo steel by niobium or vanadium singly or in combination
resulted in higher guaranteed elevated temperature yield stress (250–280 MPa). The final rolling temperature
should be maintained above austenite recrystallization stop temperature (~

900° °C) to minimize dislocation
hardening. In a quenched and self-tempered 600 MPa class TMT reinforcement bar steel (YS: 624 MPa), low
chromium (0⋅ ⋅55%) addition produced the requisite yield stress at 600° °C. The low-alloy fire resistant steel will
have superior thermal conductivity up to 600° °C (>

30 W/m⋅ ⋅k) compared to more concentrated alloys.

Keywords. Fire resistant steel; thermomechanical processing; microstructure; strength; thermal conductivity.
1. Introduction
Steel structures using mild steel in fire sensitive areas are
protected from fire by providing fire resistant coating or
insulation. This adds to the constructional cost. The problem
with unprotected carbon–manganese mild steel is its poor
strength at temperatures above ~

350°C, which can make
a structure unsafe after a major fire. In case of short duration
fire, it is rather difficult to assess the damage to structures
caused by fire and may call for demolition/renovation of the
structures. Most of the research efforts relating to construction
in fire sensitive areas were directed towards development
of steels that can retain adequate strength after prolonged
exposure in fire. The building codes of some specifications
require the steel to have a minimum of one-half (ASTM
1996) to two-thirds (Fushioni et al 1995; BIS 2002) of room
temperature yield strength at 500–600°C compared to the
mild steel which retains about one-third of room temperature
yield strength at 600°C. In order to achieve this strength
level, the steel chemistry and manufacturing process are
closely controlled. Previous studies on microstructure and
mechanical properties of fire resistant steels carried out
by Chijiwa et al (1993) and Assefpour-Dezfully et al (1990)
focussed on processing, structure and properties of fire
resistant steels with different combinations of alloying
elements. In the present investigation, the effect of lower
alloying addition, particularly molybdenum, on the elevated
temperature properties will be discussed which is important
due to increasing alloy cost. Over and above, there is hardly
any information on alloying required to obtain two-thirds
of room temperature yield stress at 600°C for thermome-
chanically treated (TMT) rebar particularly, the high strength
variety with yield strength above 600 MPa. The present
work was carried out to ascertain minimum requirement of
molybdenum/chromium in steels with and without micro-
alloying elements in order to achieve the guaranteed
strength at 600°C in plate, structurals and TMT rebar and
their effects on structure and properties.
2. Experimental
Six experimental laboratory heats (steels A–F) and one
industrial heat (steel G) were melted in 0⋅1 T air induction
(IF) and 6 T electric arc furnace (EAF), respectively for proce-
ssing to plate and beam. The ingots from IF heats were
soaked at 1250°C for 2 h and thermomechanically processed
(TMP) in an experimental rolling mill to 12–14 mm thick
plates in nine passes. The ingot from EAF heat was soaked
at 1320°C for 4 h and rolled to blooms of size 230 ×
160 mm. These blooms were soaked at 1250°C and sub-
sequently thermomechanically processed to 200 × 100 mm
beam section. The finishing rolling temperatures (FRT)
for plates and beam were measured with an infrared pyrome-
ter up to an accuracy of ± 5°C and were between 800 and
925°C. The finishing pass reduction was 20–30% for plates
and about 10% for beam. The plates and beam were allowed
to cool in natural air after rolling. Another heat (steel H)
was made in 250 T twin hearth furnace and cast as 9 T
ingots for processing to TMT rebar. The ingots were rolled
to billets of size 100 × 100 mm after soaking at 1300°C
for 4 h. These billets were subsequently reheated at 1250°C

(panigrahi@sail-rdcis.com)
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Bimal Kumar Panigrahi

60
and processed to TMT rebar of 32 mm diameter through a
Thermex cooling system.
Round tensile specimens (dia. 6⋅25 mm) were machined
from the quarter width position of the plates (width of
plate: 135 mm) in the longitudinal direction as per ASTM A
370 standard and tested at room temperature (30°C) and
at elevated temperatures up to 600°C at cross head speed of
2 mm/min in a servohydraulic test machine as per ASTM
E 8 and E 21 standards, respectively. Tensile testing of
plates was also carried out selectively at room tempera-
ture after exposure at 600°C for 3 h under applied stress
of 140 MPa. The specimens after exposure were allowed to
cool to room temperature inside the furnace. In the elevated
temperature test of plates the specimens were heated from
room temperature to the test temperature and soaked at
the desired temperature for 15 min before tensile stress
was applied. The accuracy of the test temperature was con-
trolled within ± 1°C. Charpy V-notch impact test specimens
of size 10 × 10 × 55 mm from steels A–F were machined
across the plate width in the longitudinal direction and
tested at RT to –

30°C as per ASTM E 23 standard. The
optical microstructure was examined in the longitudinal
through thickness direction after polishing and etching by
2% nital. The average grain size was measured by linear
intercept method. Transmission electron microscopic (TEM)
investigation was carried out using thin foils prepared
from mechanically thinned strip of thickness below 0⋅1 mm.
The electropolishing was done in a twin jet polisher using
a solution of 5% perchloric acid and 95% glacial acetic
acid at 20°C and 60V operating voltage. The foils were
observed at 200 keV.
Flat tensile specimens (gauge length: 5⋅65 √area) were
prepared in the longitudinal direction from the web of the
beam as per IS 2062 standard (BIS 1998). The ambient
and elevated temperature tensile testing was conducted as
described for plates. Tensile testing was also done after
an aging treatment at 600°C for 3 h under applied tensile
stress of 140 MPa. Charpy V-notch specimens (size
7⋅5 × 10 × 55 mm) were prepared from the flange region
as described in IS 2062 standard and tested as described
for plate in the longitudinal direction. The optical micro-
structure was examined in the longitudinal through thickness
direction after polishing and etching by 2% nital. The
average grain size was measured by linear intercept method.
TEM specimens were prepared from the flange region as
described for plate and observed at 200 keV. Full scale
fire resistance test was carried out on beam section (size
200 × 100 × 3900 mm) as per ASTM E 119 standard (ASTM
1996) at Fire Research Laboratory, CSIR, Roorkee, India.
The bare beam was mounted on the specimen frame
holder of a gas fired furnace. The furnace was rectangular in
shape. The casing was made up of steel reinforced sec-
tions. The refractory lining of the furnace consisted of
front layer of kyanite insulation bricks backed by hot face
insulation. The burner casing was made up of fire bricks.
The complete furnace assembly consisted of four walls
and the open roof top for mounting the beam specimen.
The flue gas for heating passed through a duct surrounding
the sides of the walls and then was disposed off through a
chimney. There were ten long flame burners. The capacity
of each burner was 35–40 l/h. The furnace was run on positive
pressure. The heating of the specimen was done as specified
in ASTM E119 standard. The thermocouples were fixed
at four different sections of the beam to measure the rise
of temperature at different intervals. While plotting the tem-
perature vs time curves, average temperature measured by
concerned thermocouples in a section was used.
Tensile testing of rebar was done using unmachined
rebar (gauge length: 5 dia.) at ambient temperature in a
60 T servo hydraulic tensile testing machine at a cross
head speed of 10 mm/min. For the elevated temperature
test at 600°C, round specimens were used from the core
region of rebar and tested as described for plate material.
Charpy V-notch impact specimens were also prepared
from the location described previously (Panigrahi and
Jain 2002) and tested similar to plate. The optical micro-
structure was examined in the transverse section after
polishing and etching by 3% nital. TEM specimens were
prepared from the rim and core regions of the rebar as
described for plate and observed at 200 keV.
3. Results and discussion
3.1 Chemical composition
In a structural steel, the composition will be determined
by the requirement of strength, toughness and weldabi-
lity. The chemical composition of steels is given in table 1.
The carbon was 0⋅11–0⋅13% in plate, 0⋅17% in structural
beam and 0⋅25% in TMT rebar. The conventional way to
improve moderately the strength at elevated temperature
(up to ~

350°C) is by increasing the carbon content (Houdre-
mont 1953). Lower carbon in hot-rolled steel improves
notch toughness and weldability. In TMT rebar carbon
increases the hardenability. Manganese increases the strength
by solid solution hardening (Baird and Jamieson 1972) in
hot rolled steel. Manganese tends to lower the eutectoid
carbon content in steel and promotes segregation particu-
larly in hot rolled structural steel with carbon >

0⋅10%.
This can adversely affect the mechanical properties. Manga-
nese was restricted to 1% in fire resistant hot rolled plate
and structural with carbon 0⋅10–0⋅20% and 1⋅5% in TMT
rebar where manganese is a potential hardenability en-
hancing element. Silicon content in steels A–G varied
from 0⋅29–0⋅35%. Silicon is a solid solution strengthener
and a deoxidizer. Silicon retards softening at high tem-
peratures (Irvine 1962) and also increases the hardenability.
However, in steel H, its content was low due to tech-
noeconomic reasons. The aluminium (0⋅01–0⋅02%) is
required to tie-up free nitrogen to improve toughness. In
the steels A, D, E and F, the content of aluminium was
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61
Table 1. Chemical composition of steels (wt.%).
Steel A B C D E F G H

C 0⋅11 0⋅12 0⋅12 0⋅13 0⋅13 0⋅12 0⋅17 0⋅25
Mn 1⋅02 1⋅02 1⋅08 0⋅99 1⋅00 0⋅96 0⋅74 1⋅42
Si 0⋅35 0⋅35 0⋅29 0⋅31 0⋅31 0⋅30 0⋅31 0⋅056
S 0⋅022 0⋅032 0⋅029 0⋅025 0⋅026 0⋅025 0⋅034 0⋅024
P 0⋅019 0⋅025 0⋅027 0⋅021 0⋅022 0⋅021 0⋅027 0⋅024
Cr 0⋅31 0⋅29 0⋅40 0⋅38 0⋅39 0⋅38 0⋅54 0⋅55
Mo 0⋅26 0⋅20 0⋅14 0⋅26 0⋅26 0⋅26 0⋅22 –
Nb – – – 0⋅02 – 0⋅02 – –
V – – – – 0⋅07 0⋅12 – –
Al 0⋅0033 0⋅099 0⋅097 0⋅0034 0⋅0039 0⋅0039 0⋅052 0⋅004
N 0⋅0042 0⋅0063 0⋅0067 0⋅0047 0⋅0047 0⋅0070 0⋅0124 0⋅0075


lower than the prescribed range. The rebar steel was
semi-killed. Chromium in small percent forms (FeCr)
3
C
(Houdremont 1953) in the cementite of pearlite. It is a
ferrite stabilizer and increases the hardenability. However,
its potential as a solid solution strengthening element is
small due to its high affinity to carbon. The amount of chro-
mium was 0⋅29–0⋅40% in plate and 0⋅55% in structural
beam and TMT rebar. Molybdenum increases elevated
temperature yield strength (Argent et al 1970; Honey-
combe 1981) even when present in small percent (~

0⋅25%)
in solid solution in low carbon steel. It also forms carbide
(Fe, Mo)
3
C in the cementite of pearlite resisting softening
on prolonged exposure in a fire (Houdremont 1953). Molyb-
denum tends to hinder self-diffusion of iron (Houdremont
1953), thus increasing the recrystallization temperature of
steel. Microalloying elements, vanadium and niobium,
increase the elevated temperature strength (Pickering 1978;
Sage 1983). They also increase the recrystallization tempera-
ture of steel (Borato et al 1988). Their carbides also offer
resistance to softening when the steel is exposed to fire.
The chemistry of the present investigation differs from
the previous studies (Assefpour-Dezfully et al 1990; Chi-
jiwa et al 1993; Fushioni et al 1995) in the following
ways: (a) the content of molybdenum and chromium is
low, (b) low niobium and vanadium are used in micro-
alloyed steels and (c) chromium without molybdenum has
been used in TMT rebar.
3.2 Thermomechanical processing (TMP)
Processing plays an important role since it determines the
final microstructure and mechanical properties of hot
rolled steel (Panigrahi 2004). The TMP schedule for plate
and beam is shown in figure 1. TMP of plate and beam
involves controlled deformation of austenite at higher
temperatures above the recrystallization stop temperature
(t
nr
) (Borato et al 1988) during which static and dynamic
restoration processes occur (Tanaka 1981). Table 2 shows
data on total reduction, approximate recrystallization stop
temperature, finishing temperature and grain size of steels.
As the finish rolling temperatures (FRT) of all steels ex-
cept steel F and a few structurals of steel G were above t
nr
,
an equiaxed ferrite microstructure could be obtained with
low dislocation density. Steel F was finish rolled at 800°C,
quite below t
nr
(884⋅1°C) but above Ar
3
temperature (771°C)
(Ouchi et al 1982). Deformation in this region strain
hardened the austenite, increasing its dislocation density.
Deformation bands are also formed (Tanaka 1981). Since
ferrite nucleates both on austenite grain boundaries and
deformation bands, the grains are finest (7⋅7 µm). How-
ever, the cellular structure retained by rolling below t
nr
,
lowered the yield strength at elevated temperatures.
In the processing of TMT rebar (figure 1), initially at
higher temperatures (1200–1100°C) the material recrys-
tallizes statically. At the intermediate and finishing stages
of processing (1000–1050°C), static, dynamic as well as
metadynamic recrystallization of austenite can occur (Poliak
and Jonas 2003) depending upon strain at different passes
producing an equiaxed austenite structure. On leaving the
finishing stand at 1000–1050°C, the bar enters a Thermex
cooling chamber where the surface of the bar is cooled by
pressurized water at ~

200°C/s forming a thin rim of lath
martensite while the core is still austenite. On emergence
from the cooling chamber, the martensite rim gets self-
tempered by the heat of the core and the core finally
transforms to bainite.
3.3 Microstructure
Typical optical microstructures of some steels in as-rolled
condition are shown in figure 2. The Cr–Mo (steel A) and
Cr–Mo–Nb (steel D) alloyed plates (figures 2a and b) and
beam (figure 2c) showed a predominantly polygonal fer-
rite–pearlite microstructure. At higher magnification, steel
A (figure 2d) also showed upper bainite (arrow mark). The
bainite in steel A resembles pearlitic bainite (Bhadeshia
1992) as the colonies tend to have crystallographic facets
rather than nicely rounded colonies of conventional pear-
lite. The vanadium (steel E) and niobium plus vanadium
(steel F) microalloyed steels also showed similar micro-
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Bimal Kumar Panigrahi

62

Figure 1. Schematic of TMP schedule for plate, beam and TMT rebar (M, martensite; γ, austenite).


Figure 2. As hot rolled microstructures of a. Cr–Mo plate (steel A), b. Cr–Mo–Nb plate
(steel D), c. Cr–Mo beam (steel G) and d. pearlitic bainite of Cr–Mo plate (steel A).

Table 2. Process parameters and microstructural data.
Thickness Total FRT Grain size
Steels (mm) reduction (%) t
nr
(°C) (°C) Structure (µm) Product

A 14 86 814⋅0 900 F + P + B 10⋅4 Plate
B 12 88 853⋅5 900 F + P 13⋅5 Plate
C 12 88 874⋅3 900 F + P 12⋅5 Plate
D 12 88 876⋅9 900 F + P + B 11⋅0 Plate
E 12 88 828⋅5 875 F + P + B 12⋅5 Plate
F 12 88 884⋅1 800 F + P + B 7⋅7 Plate
G – 94* 874 850–925 F + P + B 10⋅3 Beam
H – 92 984⋅4 1000 M + B – Rebar
F, Ferrite; P, pearlite; B, bainite; M, tempered martensite; *flange region; t
nr
= 887 +
464%C + (6645%Nb−664√%Nb) + (732%V−230√%V) + 890% Ti + 363%Al−357%Si.
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Fire resistant steel

63

Figure 3. Bright field TEM of a. Cr–Mo–Nb–V plate (steel F), b. and c. Cr–Mo beam (steel G) and d. TMT rebar.


structures. The bainite ‘colonies’ in steel G were coarser
than steels A, D, E and F and were more numerous possi-
bly due to presence of somewhat higher carbon and
chromium in this steel, lower reduction per pass and
coarser austenite grains prior to transformation. The bainite
was not observed in steels B and C. The finishing rolling
in the austenite region above recrystallization stop tempera-
ture helped to form polygonal ferrite grain structure in
Cr–Mo, Cr–Mo–Nb and Cr–Mo–V plate steels. In this
case ferrite nucleates on austenite grain boundaries (Tanaka
1981). Cr–Mo–Nb–V plate (steel F) was finish rolled in
the unrecrystallized austenite region producing grain size
finer than other steels (table 2) due to nucleation of ferrite
on austenite grain boundaries, transgranular twins and
deformation bands (DeArdo 1995; Panigrahi 2001) after
transformation. The partial cellular structure of steel F
with dislocations retained is shown in figure 3a. The beam
steel also showed upper bainite (figure 3b) with cementite
particles distributed between ferrite platelets (figure 3c).
An exposure treatment up to 3 h at 600°C did not show
changes in the appearance of microstructure. Unlike
martensite in which dissolved carbon in solid solution is
high, bainite has little carbon in solid solution and is
much less sensitive to tempering at low temperatures
(~

600°C). However, cementite particles can coarsen and
a general recovery of dislocation substructure occurs
(Bhadeshia 1992). The TMT rebar steel showed a tempered
martensite rim. The core structure was bainitic (figure 3d)
due to high hardenability of this steel.
3.4 Elevated temperature yield stress
The dependence of yield stress and UTS with temperature
for steels A–G is shown in figure 4. Steel F showed a
faster drop of yield stress after 500°C. However, except
steel C (0⋅14%Mo) whose yield stress was marginally
below the desired level at 600°C, all other steels retained
two-thirds of their room temperature yield strength at
600°C (table 3). The elevated temperature yield stress de-
pends mainly on the stability of microstructure at higher
temperatures. Chromium and molybdenum have a stabi-
lizing effect on cementite of pearlite (Houdremont 1953).
A higher amount of chromium in steel C prevented exce-
ssive drop of yield stress at 600°C despite low molybdenum
(0⋅14%) in it. Steels D and E that are microalloyed with
Nb and V, respectively have highest level of yield stress
at 600°C viz. 82% and 85%, respectively. Nb and V have
added advantages due to their precipitation hardening
potential and the loss of strength at higher temperature is
minimal. The rapid drop of yield stress of steel F above
500°C was due to lowering of dislocation density on
soaking above 500°C. The UTS of all steels fell sharply
above 400°C (figure 4). The elongation of all steels at
600°C was higher than elongation at the ambient tem-
perature. Exposure at 600°C for 3 h increased the yield
stress by about 50 MPa without significant change in
elongation in steels A, D, E, F and G. The core of rebar steel
H with bainitic structure also showed two-thirds of room
temperature yield stress at 600°C (table 3). Due to presence of
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Bimal Kumar Panigrahi

64

Figure 4. Dependence of (a) yield stress and (b) UTS on temperatures of fire resistant steels and mild steel (MS).


Table 3. Tensile properties of the investigated steels.
Steel A B C D E F G H

Ambient temperature (RT)
YS (MPa) 287 293 298 338 293 415 320 624
UTS (MPa) 505 486 539 582 530 622 541 819
El. (%) 38⋅0 36⋅2 32⋅0 30⋅0 37⋅8 26⋅8 27⋅3 12⋅5
Elevated temperature (600°C)
YS (MPa) 219 191 188 279 250 280 214 419
UTS (MPa) 326 259 247 332 327 338 292 426
El. (%) 42⋅2 41⋅7 49⋅0 40⋅4 36⋅2 46⋅0 33⋅0 30⋅5
% of room temperature YS 76⋅3 65⋅1 63⋅0 82⋅5 85⋅3 67⋅4 66⋅8 67⋅1
After thermal exposure at 600°C under applied stress
YS (MPa) 360 – – 408 348 469 369 –
UTS (MPa) 432 – – 523 475 584 492 –
El. (%) 22⋅5 – – 30⋅8 34⋅0 22⋅8 27⋅0 –


tempered martensite rim, the overall strength of TMT
rebar at 600°C should be higher than two-thirds of its
room temperature yield strength. In a composite micro-
structure comprising tempered martensite rim and bainitic
core, the overall yield stress is given by area fraction of
rim multiplied by yield stress of rim plus area fraction of
core multiplied by yield stress of core. The area fraction
of bainite core was 0⋅766 and that of tempered martensite
rim was 0⋅234. Previous investigation (Panigrahi 2002)
showed that low-alloyed tempered martensite structure
had more than two-thirds of room temperature yield
stress at 600°C.
3.5 Impact toughness
The ambient temperature impact toughness, 50% energy
ductile brittle transition temperature (DBTT) (Dahl 1992)
and fracture characteristics are given in table 4. The upper
shelf energy of as-rolled plate and beam varied from 65–
118 J (figure 5). The steels A, D, E and F showed DBTT
at –

4°C to –12°C. The DBTT of steel B was below –30°C
and that of steel C was –28°C. Presence of upper bainite
in all steels except steels B and C, low aluminium content
(steels A, D, E and F) and cellular structure (steel F)
were responsible for increase in DBTT. Notwithstanding
Temperature (°C)
Temperature (°C)
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Fire resistant steel

65
higher carbon content, steel H showed a DBTT of –14°C
due to presence of tempered martensite and some acicular
ferrite in it. Steel G showed a DBTT of –5°C in as rolled
condition and –34°C in aged condition. The DBTT of
steel G in as rolled condition was higher than steel A possibly
due to presence of relatively coarser ‘colonies’ of pearlitic
bainite in its microstructure and a higher carbon content
(0⋅17%) (Pickering 1978) compared to steel A (0⋅11%



Figure 5. Charpy energy vs temperature curves of plates and
beam.



Figure 6. Typical time–temperature curves for Cr–Mo beam
(steel G) and mild steel (T
1
, T
2
and T
3
are locations of thermo-
couples at section 1).
carbon). On exposure at 600°C, the improved toughness
(DBTT: –34°C) of steel G could be due to lowering of
dislocation density of bainite and diffusion of embrittling
atoms present on the grain boundaries to the dislocations.
Improvement of impact transition temperature by diffusion
of phosphorus from prior austenite grain boundaries to
lattice defects was reported earlier for spring steel (Wettlaufer
and Kasper 2000). However, upper shelf energy of aged
steel was lower than the as-rolled beam possibly due to
microstructural heterogeneity leading to formation of local-
ized carbide rich areas that aided lowering of the absorbed
energy.
3.6 Fire resistance
The average temperature rise of fire resistant steel (FRS)
beam and mild steel (MS) beam (0⋅17C, 0⋅69Mn, 0⋅04Si,
0⋅048S, 0⋅028P, 0⋅007Al) is shown in figure 6 for section


Table 4. Charpy toughness data.
Toughness at RT DBTT Fracture
Steel (Joule) (°C) surface at RT

A 118 −

12 Dimple
B 116 <−

30 Dimple
C 100 −

28 Dimple
D 94 −

9 Dimple
E 82 −

8 Dimple
F 73 −

4 Dimple
G (as rolled) 87 −

5 Dimple
G (after thermal exposure 50 −

34 Dimple
at 600°C)
H 88 −

14 Quasi cleavage
Note: All values of toughness are for full size specimens.



Figure 7. Dependence of thermal conductivity of dilute steel
alloys on temperatures.
Temperature (°C)
T
e
m
p
e
r
a
t
u
r
e

(
°
C
)

Temperature (°C)
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Bimal Kumar Panigrahi

66
1 (inset). The rise of temperatures up to 600°C for other
sections was similar to section 1. It was observed that the
temperature of the fire resistant steel was at a lower level
compared to mild steel. The data points for these curves
remain below the ASTM E 119 standard time–temperature
curve in a fire test (ASTM 1996). The time to reach the
critical temperature (538°C) was 32 min and 21 min for
fire resistant steel and mild steel, respectively. The rate of
heating is dependent on the thermal conductivity which is
a material property governing the flow of heat through a
material at steady state. Figure 7 shows the dependence
of thermal conductivity with temperature for pure iron
and some constructional steels (Riemann 1953; McGannon
1966). The thermal conductivity of pure iron and dilute
alloys decreases with rising temperature. The likely be-
haviour of 0⋅5Cr–0⋅22Mo fire resistant steel which is a
dilute alloy is also shown in this figure. Its conductivity
should be higher than 30 W/m⋅k at 600°C. The dominant
carrier of the thermal conduction in pure metals and dilute
alloys is electrons (Ho et al 1975; Isachenko et al 1980;
Touloukian and Ho 1981; Landolt 1991). When small
amount of alloying elements (impurities) are introduced
in iron, it causes discontinuities in the crystal lattice struc-
ture and promotes scattering of free electrons decreasing
the room temperature thermal conductivity (Riemann 1953;
McGannon 1966). With rising temperature, the scattering
of free electrons is intensified (Isachenko et al 1980). This
causes a net reduction of thermal conductivity at higher
temperature. Even then the thermal conductivity of dilute
steel alloy is still high (>

30 W/m⋅k) at 600°C. Since in a
fire, temperature gradients are encountered, a high ther-
mal conductivity material is desired to avoid degradation
by local necking.
4. Conclusions
Small additions of Mo (0⋅20–0⋅25%) and Cr (0⋅30–0⋅55%)
in low carbon steel produced hot rolled fire resistant steel
with a minimum of two-thirds of room temperature yield
stress at 600°C. Microalloying by niobium and vanadium
improved the ratio of YS
600°C
/YS
RT
. However, final rolling
temperature should be maintained in the recrystallized
austenite region to ensure a microstructure free from high
dislocation density. The steels should be adequately treated
by aluminium to tie-up free nitrogen in order to realize
lower DBTT. In the quenched and self-tempered TMT
rebar steel, addition of ~

0⋅55% chromium was adequate
to ensure the guaranteed strength at 600°C due to transforma-
tion to tempered martensite rim and bainitic core. Despite
decreasing trend of thermal conductivity with the rise of
temperature in dilute alloys, the low alloy fire resistant
steel will have higher thermal conductivity up to 600°C
(>

30 W/m⋅k) compared to more concentrated alloys and
is less expensive.
References
American Society of Testing Materials 1996 Standard test
methods for fire tests of building construction and materials,
Philadelphia, E119
Argent B B, Niekenk M N and Redfern G A 1970 J. Iron &
Steel Inst. 208 830
Assefpour-Dezfully M, Hugas B A and Brownrigg A 1990 Mater.
Sci. & Technol. 6 1210
Baird J D and Jamieson A 1972 J. Iron & Steel Inst. 210 847
Bhadeshia H K D H 1992 Bainite in steels (London: Institute of
Materials)
Borato F, Barbosa R, Yue S and Jonas J J 1988 Proc. Thermec’88
(ed.) I Tamura (Tokyo: Iron and Steel Inst. Japan) p. 388
Bureau of Indian Standards 1998 Indian Standards IS 2062,
New Delhi
Bureau of Indian Standards 2002 Indian Standards IS 15103,
New Delhi
Chijiwa R, Tamehiro H, Yoshida Y, Funato K, Uemori R and
Horii Y 1993 Nippon Steel Tech. Report 58 47
Dahl W 1992 Steel (Dusseldorf: Springer Verlag and Verlag
Stahl Eisen) 1
DeArdo A J 1995 Microalloying’95 (Warrendale: Iron and Steel
Society) p. 15
Fushioni M, Chikaraishi H and Keira K 1995 Nippon Steel Tech
Report 66 29
Ho C Y, Powell R W and Liley P E 1975 Thermal conductivity
of the elements: A comprehensive review (NewYork: AIP)
Honeycombe R W K 1981 Steel microstructure and properties
(London: Edward Arnold; Ohio : ASM)
Houdremont E 1953 Handbook of special steels (Berlin:
Springer Verlag) 1
Irvine K J 1962 J. Iron & Steel Inst. 200 820
Isachenko V P, Osipova V A and Sukomel A S 1980 Heat
transfer (Moscow: Mir Publisher)
Landolt B 1991 Thermal conductivity of pure metals and alloys
(eds) O Madelun and G K White (Berlin: Springer Verlag)
15C
McGannon H E (ed.) 1966 Making, shaping and treating of
steels (Pittsburgh : USS)
Ouchi C, Sampei T and Kozasu I 1982 Iron & Steel Inst., Japan
22 214
Panigrahi B K 2001 Bull. Mater. Sci. 24 361
Panigrahi B K 2002 Unpublished result
Panigrahi B K 2004 Seminar on Structural steel for construction
industry (NIT, Rourkela: The Institution of Engineers)
Panigrahi B K and Jain S K 2002 Bull. Mater. Sci. 25 319
Pickering F B 1978 Physical metallurgy and design of steels
(London: Applied Science Pub.)
Poliak E I and Jonas J J 2003 Iron & Steel Inst. Japan Int. 43
692
Riemann W 1953 Stahl und Eisen 73 721
Sage A M 1983 Proc. int. conf. steels for line pipe and pipe line
fittings (London: Metals Soc.) p. 39
Tanaka T 1981 Int. Metal. Rev. 26 185
Touloukian Y S and Ho C Y 1981 Properties of selected fer-
rous alloying elements (New York: McGraw Hill Book Co.)
III.1
Wettlaufer M and Kasper R 2000 Steel Res. 71 357

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Some Fundamental Steps in Thermomechanical Processing
of Steels* .
By Imao TAMURA**
Key words: ~hermomechanicalprocetsing; steel; deformation o f austenite;
restoration process; phase transformation; microalloying; f erri t e grai n re-
Jinement.
I. Introduction
Thermomechanical processing is a treatment of
which plastic deformation is introduced into the heat
treatment of steel. We can find many treatments in
such processes. But controlled rolling and acceler-
ated cooling, and the ausforming or deformation-
quenching are representative and are used in practical
production.
I n controlled rolling, the austenite (y) is work-
hardened with plastic deformation (rolling) in high
strain rate at elevated temperatures, and then air
cooled to transform to ferrite (a). Sometimes, work-
hardened austenite is cooled acceleratedly to take fine
ferrite grains in steel plate.
-
In the ausforming, work-hardened austenite is
quenched to room temperature. We can take the
ausformed martensite which increases its strength and
not decrease its toughness. The ausforming is not so
popular in practice but the deformation-quenching is
getting to be popular. The martensite in the defor-
mation-quenching looks like as usual martensite. But,
this martensite has a little bit of fine facet size be-
cause it is formed from smaller austenite grains than
usual austenite. This process can abridge to ration-
alize the heat treatment process of steel.
As fundamental steps in thermomechanical proc-
True strain
tn
3
Fig. 1. Schematic illustration of two types of true stress-
true strain curves accompanying the steady state
deformation at elevated temperatures.
( a)
dynamic recovery
essing of steels, we can point out that:
1)
The deformation and restoration processes of y
during and after hot rolling.
2)
The kinetics of y to a transformation and grain
size of a.
3)
The effect of cooling rate on transformation of
work-hardened y to a, and grain size of a.
4)
Structure of martensite in ferrous alloys.
5)
Structure and properties of martensite formed
from work-hardened y.
6)
Hardenability of work-hardened y and recrystal-
lized y.
I will explain on these processes based on our re-
search results.
(b) dynamic recrystallization
II. Deformation Behaviors of Austenite during
and after Hot Working
I . Restoration Process during Hot Deformation of Auste-
I t is well known that the deformation behavior of
austenite at elevated temperatures is a dynamic re-
crystallization type. Figure 1 shows schematically
both types of dynamic recovery type and dynamic
recrystallization type.
I n the case of a dynamic recrystallization type,
since the rate of softening due to recovery is slow, the
work-hardening can not be balanced only by dynamic
recovery even at high temperatures, and the disloca-
tion density is still gradually increased with strain,
and finally the recrystallization starts to occur during
deformation. The true stress is lowered beyond the
peak stress by the occurrence of dynamic recrystal-
lization and reaches a certain steady state stress
level at which the work-hardening and softening due
to recrystallization occurring repeatedly are balanced.
The dynamic recrystallization starts at the strain of
around 0.78, (E,: the strain showing the peak stress).
In Fig. l(b), the strain range up to about 0 . 7 ~ ~ is
the work-hardening region, the strain range between
about 0.78, and 8, (the strain at which the steady
state deformation starts) is the range of partially
dynamic recrystallization, and the strain range after
E , ~ is the range of steady dynamic recrystallization.
Austenite in steels belongs to this type. In a-Fe (fer-
rite), since the recovery occurs very fast, the restora-
tion is performed mainly by dynamic recovery. The
peak stress (a,) and the steady state stress (a,) in the
dynamic recrystallization type change with the Zener-
*
Based on the Special Lecture delivered by Prof. Tamura in commemoration of his receiving Nishiyama Medal in the 113th ISIJ
Meeting, April 2, 1987, at The University of Tokyo in Tokyo. Manuscript received on May 18, 1987. 0 1987 ISIJ
* * Professor Emeritus, Kyoto University; Technical Advisor, Sumitomo Metal Industries, Ltd., Nishinagasu-hondori, Amagasaki 660.
Special Lecture ( 763 )
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[ 764 ) Transactions ISIJ, Vol. 27, 1987
Hollomon parameter (2). Z is expressed by
where, i: the strain rate (s-l)
I? : a gas constant (J/mol)
Q:
the activation energy for deformation (J/
mol)
7: temperature (K).
a?,, ep, gs and E , are increased with increase in Z (i.e.,
with increase in i or decrease in 7).
Figure 2 shows the change in optical microstructure
with strain in Fe-31%Ni-0.3%C austenitic alloy
which was tensile deformed at 1 273 K (1 000°C) at a
strain rate of 1.7 x 10-2/s. Figure 2(a) is the austenite
structure before deformation. Austenite grains are
equiaxed and their boundaries are smooth and planer.
Many annealing twins exist in austenite grains. When
deformed slightly (E= 0.08), as shown in Fig. 2 (b), the
grain boundaries become finely serrated and the bulg-
i n g ~ of grain boundary are observed as indicated by
the arrows. At the strain slightly after E,, many small
grains are newly formed along the austenite bound-
aries as shown in Fig. 2(c). It is characteristic that
these newly formed grains hardly contain annealing
twins. Furthermore, some of the initial austenite
grains becomes larger by the strain-enhanced coarsen-
ing. Figure 2(d) shows the structure in the range of
steady state deformation at which the work-hardening
and the dynamic recrystallization softening are bal-
anced. This structure consists of several grains cor-
responding to various stages of recrystallization, i.e.,
from small grains which have just started to recrys-
tallize to fairly large grains which have been subjected
to deformation after the finishing of recrystallization
and are the work-hardened state just before the next
recrystallization. I n the stage of steady state defor-
mation, the recrystallization occurs repeatedly during
deformation. Dynamic recrystallized grains contain
a few annealing twins at low Z but scarcely contain
them when Z is high.
I n the same way as the static recry~tallization,~) it
has been observed that there are two main mech-
anisms for dynamic recrystallization, i.e., the bulging
mechanism and the nucleation-growth mechanism.
Dynamic recrystallization becomes easier to take
place when the initial grain size (do) of austenite is
smaller. Therefore, in the case of fine initial grain
size, c p and E, become small even at the deformation
under the same Z condition. However, a,, and a , are
independent of do. The average size (d) of dynam-
ically recrystallized grains is the only function of Z
and is expressed by the following equation,')
where, A, : material's constant.
A is larger for C-steel than for alloy steels, especially
small for Nb-containing steel and high alloy steel. p
is about 0.3-0.4 for all steels. It should be noted
that d is independent of do.
2. Static Restoration Process during Holding Right after
Hot Deformation
When the hot deformation is finished at the work-
hardening stage, the work-hardened austenite is sof-
tened by the usual static recrystallization during iso-
thermal holding after deformation. However, if the
strain is too small, the recrystallization can not occur
and only the recovery takes place. On the other
hand, when specimens are isothermally held after de-
formation to the range of the steady state deformation,
in which the dynamic recrystallization has occurred,
the recrystallization and the grain growth can succeed
to occur continuously during holding after hot defor-
mation. Such a recrystallization is called a meta-
dynamic or postdynamic recrystallization. Namely,
the dynamically recrystallized structure is further
softened by the metadynamic recrystallization. When
specimens are deformed to the range of (11) in Fig.
(a) Before testing (E=O)
(b) € =0.08
(c) e=0.24
(d) &=0.40
Pig. 2. Optical micrographs showing tlie formation process of dynamically recrystallized austenite in Fc-31Ni-0.3C
austenitic alloy deformed at 1 OOO°C, 1.7 x 10-2/s.
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( 765 )
l (b) in which the work-hardened austenite and dy-
namically recrystallized austenite have coexisted, the
static recrystallization occurs in work-hardened aus-
tenite and the metadynamic recrystallization occurs
in dynamically recrystallized austenite at the same
time.
I n case of rolling by hot strip mill in which slabs
are rolled by several passes, the static restoration proc-
ess occurring during interval between rolling passes
has great influence on the deformation behavior of
next rolling pass. If the softening due to the static
restoration is not completed during interval between
rolling passes, the work-hardening is successively ac-
cumulated by the subsequent rolling passes.
Fraction of softening (X) occurring during iso-
thermal holding right after hot deformation can be
evaluated by the two-step deformation test from the
following e q~a t i on, ~)
where, cr,,,: the flow stress immediately before un-
loading
c ~ , , ~ : the yield stress on reloading after hold-
ing the specimen for various periods of
time (At)
u,,, :
the initial yield stress.
As an example, the change in the fractional softening
(X) with the holding time (At) in Fe-31 %Ni-O.S%C
austenitic alloy is shown in Fig. 3. Specimens were
tensile deformed at 1 373 K (1 100°C) at a strain rate
of 4 x 10-2/s to E = 0.18 (work-hardened austenite) and
e= 1.0 (completely dynamically recrystallized auste-
nite), respectively, and then isothermally hild for
various periods of time. The change in average aus-
tenite grain size with At is also plotted in Fig. 3.
Microstructural changes during isothermal holding at
1 373 K (1 100°C) are shown in Fig. 4 and Fig. 5.
As shown in Fig. 4 (~=0. 18), work-hardened austenites
are slightly elongated along the tensile direction (Fig.
4(a)). The austenite hardly changes by holding for
1 s (Fig. 4(b)), although the softening occurs to some
extent by the static recovery as can be seen in Fig. 3.
However, when specimens were isothermally held for
4 s (Fig. 4(c)), fine austenite grains which are form-
ed by static recrystallization are partially formed
mainly along the deformed austenite grain boundaries
and the static recrystallization is completed by the
holding of 15 s (Fig. 4(d)). Annealing twins in static
recrystallized austenites are gradually developed with
increase in holding time. By holding for 40 s, recrys-
tallized austenite grains are coarsened (Fig. 3). When
the austenite was much more heavily deformed under
higher Z condition (work-hardened), the static re-
crystallized austenite grains become much finer as
shown in Fig. 6. As shown in Fig. 5 (a=1.0), dy-
namically recrystallized austenites are characterized
by irregular grain boundaries, a low density of an-
nealing twins and the mixed grain size. With in-
crease in holding time, austenite grain boundaries
become fairly straight and austenite structure becomes
almost equiaxed grains, and furthermore, the density
of annealing twins is increased. This is the typical
microstructural change occurring during metadynam-
ic recrystallization process. Metadynamic recrystal-
lization is completed by the holding for about 30 s in
the case of Fig. 5, and the usual grain coarsening oc-
curs by further holding. The grain size right after
the completion of metadynamic recrystallization is
smaller, as the grain size of dynamically recrystallized
Hdding time. A t (s)
Fig. 3.
Change in fraction of softening (a) and austenite As-deformed ( At = 0 S) (b) At = 1 s (c) At = 4 s (d) ~t = 15 s
grain size (b) with the isothermal holding time of Fig. 4. Change in optical microstructure of work-hardened austenite (de-
work-hardened austenite and dynamically recrystal- formed at 1 100°C, t = 4.0 x 10-2/s, c ~0 . 1 8 ) during isothermal holding
lized austcnite in Fe-31Ni-0.3C austenitic alloy. at 1 100°C for At in Fe-31Ni-0.3C austcnitic alloy.
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(a) AS-deformed ( ~ t = O s) (b) At = 1 s (c) At=2 s (d) At=30 s (a) Work-hardened austenite (detormed at 900°C,
Fig. 5. Change in optical microstructure of dynamically recrystallized austenite e=3/s, ~ z 1 . 0 )
(deformed at 1 100°C, d = 4.0 x 10-Z/s, E = 1 .O) during isothermal (h) Static recrystallized austenite (isothermally
holding at 1 100°C for At in Fe-31Ni-0.3C austenitic alloy. held at 900°C for 50 s of structure (a)
Fig. 6.
Optical micrographs showing the static recrystal-
austenite is smaller.
lization occurring during isothermal holding after
heavily work-hardened austenite in Fe-31Ni-0.3C
3. Efect of Alloying Elements on the lietardation of Re- austenitic alloy.
crystallization5)
Table 1. The values of n and m in Eq. (4) for varlous
The effect of alloying elements on the restoration
transformation conditions.
process during or after hot deformation is very im-
portant. Micro-addition of Nb or Ti acts as a re-
Mechanism Site saturation
Nucleation and
markable retardation effect on recrystallization due to
growth
-- - - - - - --
the suppression of grain boundary migration. The Site n m n m
suppression of grain boundary migration due to micro-
Grain surface 1 1 4 1
alloying is caused from (1) the solute dragging effect
Grain edge 2 2 4 2
due to segregation of alloying elements to the bound- Grain corner 3 3 4 3
aries, or (2) the pinning effect due to precipitates of
carbonitride of alloying elements at grain boundaries.
For example, Mo segregates to the austenite grain
x = l - exp [ - k ( ~ ) $ ] ..... . . . . . . . . . . (4)
boundaries, resulting in the suppression of grain
boundary migration. Even Nb micro-addition, at where, X: the transfbrmed fraction
high 1, it can retard the recrystallization by dragging
effect. But, usually, Nb and Ti are precipitated as
fine carbonitride particles and these precipitates sup-
press the grain boundary migration by the pinning
effect.
III. Transformation Kinetics and Grain Size of
Ferrite Transformed from Austenite
I . Isothermal Transformation Kinetics of Austenite
When the ferrite or pearlite Sorms from austenite
by isothermal holding below the transformation tem-
perature, these nuclei form preferentially at the prior
austenite grain boundaries. We expressed as Eq. (4)'3
that their transformation kinetics include the effect of
austenite grain size, by modification of Johnson-Mehl
equation.
t : the isothermal holding time
d: the austenite grain size
k ( 7 ) :
the rate constant which depends only
on transformation temperature and di-
rectly corresponds to the C-curve of
TTT diagram (isothermal transforma-
tion diagram).
The values oS the exponent m and n are listed in Table
1.6) These values depend on both the transformation
mechanism and type of nucleation site. Here the
transformation which progresses with nucleation and
growth over almost entire range of transformation is
called " nucleation and growth ". The transforma-
tion where all the nuclei are nucleated at the early
stage in the reaction and the progress of transforma-
tion is controlled mostly by their growth is called
" site saturation ". An austenite grain is assumed to
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( 767)
be a tetrakaidecahedra, and the nucleation sites at
austenite grain boundary can be classified into sur-
faces, edges and corners as are shown in Fig. 7.697)
Of course the actual nucleation sites are not limited to
any one of such types, and the value of m would be
the weighted average of the various nucleation sites
and not always be an integer.
According to Umemoto and Tamura,e) the values
of n and m, and transformation modes were experi-
mentally shown as in Table 2. I t is mentioned in
Table 2 that the mode of y +a transformation is site
saturation, but i t means the large number of nuclea-
tion o f a would occur at the beginning of transforma-
tion, which would not be real "site saturation ".
Sometimes the nucleation site is varied by supercool-
ing (accelerated cooling). It seems that the nuclea-
tion site of a is moved gradually from edge to surhce
by decrease in transformation temperature with cool-
ing rate, as described later.
2. Continuous Cooling Transformation Kinetics of Austenite
Scheils) considered the case where the austenite is
cooled continuously through its transformation tem-
perature. He assumed that austenite consumes its
fractional nucleation time and when the sum of a
number of such fractions equals unity, the transfor-
mation starts, i.e.,
Fig. 7. Schematic diagram of austenite grain as a tetra-
kaidecahedra and showing 3 types of nucleation
sites offerritc.
'Table 2. The values of r2 and m for various trans-
formation modes.
Transformation n m Nucleation
-
Pearlite 4 2 Edge nucleation
Nucleation and growth
1:errite 1 1 Surface nucleation near
Site saturation
Bainite 4 0. 6 Grain boundary,
Inside grain
Now extend this Scheil's additivity rule to the
entire range of transformation. I n this case the incu-
bation time ( ~ ( 7 ) ) is replaced with the time required
for the reaction to reach a certain fractional comple-
tion X by isothermal holding at temperature T. If
we combine Eq. (5) with Eq. (4)
where, Q( T) = -dT/dt: a cooling rate.
This equation expresses the transformed fraction at
temperature T during cooling from austenite condi-
tion with a cooling rate Q(T).6t9) Furthermore, from
Eqs. (4) and (6) we obtain
1 Te K(T1)1/7~
t ( 7 ) = - J - - - d T ' = t., ...... (7)
K T ) T Q(T' )
This equation tells that the fraction transformed by
cooling from 7, to T with cooling rate Q( T) is equal
to that obtained by the isothermal holding at tem-
perature T for time t ( 7) . Thus we call t ( T) as an
equivalent cooling time, t,,. t,, means the isothermal
holding time which gives the equivalent transformed
fraction with continuous cooling. The curve pro-
duced by the successive plot oS such t,, at each tem-
perature during cooling with cooling rate Q( T) will
be called an equivalent cooling curve.'O) The trans-
formation behavior for a given cooling curve can be
predicted from the TTT diagram by plotting such
curve on a TTT diagram.
3. Ferrite Grain Size Transformed from Austenite
1. Expression for Ferrite Grain Size (Isothermal)
I n general, ferrites nucleate at austenite grain
boundaries and grow into austenite grains. The
grain size of ferrite formed from austenite is directly
related with the process of transformation.") The
nominal ferrite grain diameter D, can be expressed
with the total number of ferrite grains uncleated
throughout transfbrmation per unit volume of auste-
nite, n,, as12)
where, I : nucleation rate per unit volume oS aus-
tenite
X: volume Sraction transformed
Thus the problem of obtaining the exprcssion for fer-
rite grain size is the problem of how to express n,>.
When ferrites nucleate at the austenite grain bound-
ary surfaces, they grow as ellipsoid with the aspect
ratio of 3: 113) as shown in Fig. 8. The total number
of rerrite grains nucleated per unit area of austenite
grain boundary surface is
9
n, = I,J; exp (-Tzaz~stz dt = - -
) 3:2-(':')
Nuclcation and growth
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ferrite gr a i n
gr ai n boundory
r=3Cl(t- 2)
Fig. 8. Schematic drawing of a ferrite grain nucleated at
austenite grain boundary surface.
where, I, : the nucleation rate per unit area oL aus-
tenite grain surface
a : parabolic rate constant for thickness.
The ferrite grain size D, is given as
where, Sg. b: the austenite grain surface area per
unit volume
and can be expressed by austenite grain diameter, D,,
as
Substituting Eqs. (10) and (12) into Eq. (l l ), the
ferrite grain size and the y / a transfbrmation ratio can
be expressed as
and
In the above derivation it was assumed that the
nucleation rate and the parabolic rate constant of
growth are time independent and one nuclei grows
and forms one grain.
Similarly the D, and y / a transformation ratio in the
case of homogeneous and grain edge nucleation has
been obtained asl1)
where, I h : the homogeneous nucleation rate per unit
volume
I, :
nucleation rate per unit length of auste-
nite grain edge.
I t should be noted that the equations introduced
above indicate that ferrite grain size and y/a trans-
formation ratio depend on the ratio of square root of
the nucleation rate to the parabolic rate constant in
all three types of nucleation sites. Furthermore Sor
grain boundary nucleation a small austenite grain
leads to a small ferrite grain. The effect of austenite
grain size on ferrite grain size depends on the type of
nucleation site, and it becomes large in the following
ascending order: homogeneous, grain surSaces, and
grain edges.
I t should be noted that the grain refinement on
austenite turns out to be less effective in ferrite grain
refinement. For instance in the case of grain surface
nucleation D, is proportional to D',I3 in Eq. (13).
This means that when D, is reduced to 118 of the ini-
tial, D, would be reduced only into 112.
Figure 914) shows experimental results of isothermal
transformation in a steel (0.2 % C, 0.0016 0/, B). The
steel was austenitized between 1 000 and 1200°C to
change its austenitic grain size from about 53 to 88
pm, and then transformed at 700, 680 and 660°C into
Ferrite. The results are recognized as the dependent
of y-grain diameter that a nucleates mainly at grain
edges at 700°C, at grain edges and surfaces at 680°C
and at the surfaces at 660°C.
2. Estimation of Ferrite Grain Size Formed by Continu-
ous Cooling Transformation
It can be assumed ferrite nucleates preferentially at
austenite grain surfaces by supercooling. A continu-
ous cooling transformation can be considered as the
sum of short time isothermal holdings at successive
temperatures as is schematically shown in Fig. 10.
During cooling, ferrite grains are nucleated and
grow at each temperature with the corresponding
nucleation and growth rates, as is schematically shown
in the Fig. 10 (bottom). During ferrite transforma-
tion carbon enriches in retained austenite, however,
since ferrite nucleation occurs mostly in the early stage
of transformation, it can be assumed that both the
nucleation and growth rates of ferrite are a function of
an instantaneous temperature only and not a function
of thermal history.
Based on this assumption, the number of ferrite
nuclei (N,) nucleated at temperature I, during cool-
ing, N, is given as Eq. (16).
where, Q( T) (= -dT/dt) : a cooling rate.
Ferrite grains once nucleated grow thereafter with a
corresponding growth rate at each temperature during
cooling. Thus, at temperature T, the radius of a fer-
rite grain on an austenite grain surface nucleated at
temperaturc T,, is given as Eq. (1 7).
The austenite grain boundary area occupied at tcm-
pcrature 7 by a ferrite grain nucleated at temperature
T, is given as Eq. (18).
I t will be convenient to use the concept of extended
area which is the sum of the areas of austenite grain
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( 769 ]
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Au s t e n i t e Gr ai n Size
Fig. 9. An example of D,- or D,/D,,-D, rclationsllip for
S15C steel.
surface occupied by ferrite grains, assuming that fcr-
rite grain never stop growing and that ferrite grains
keep nucleating at the same rate during transforma-
tion as well as on untransformed austenite grain sur-
faces. The extended grain boundary area occupied
by all the ferrite grains nucleated at T, during cool-
ing is given as Eq. (1 9).
Thus the grain boundary arca fraction occupied by
the ferrite grains nucleated during cooling horn A3( T, )
to T is givcn by Eq. (20).
{J:$?&; dl-' d T , ............
1 1 (2 0)
The total number of ferrite grains nucleated per unit
area of austenite grain boundary surfacc is given by
Eq. (21).
Ferrite grain size is given as Eq. (22).
o ~ * ~ ~ ~ * TI T2 T3 Tl,
d ( h ) d ( T 2 ) d( T3) ~ ( T L )
I s( T ) I s(T2) Is(T3) Is(TL )
Fig. 10. Diagrams to explain the relation between iso-
thermal and continuous cooling transformation
and schematic drawing showing the formation
process of ferrite during continuous cooling.
673 773 873 973 1073 1173
TEMPERATURE, K
Fig. 11. Calculated parabolic rate constant and nucleation
rate I, as a function of' temperature for the steel
studied. (S15C)
where, Sg.,,(=4/(dn D,)): the austenite grain surface
area pcr unit volume.
From these equations, ferrite grain s i ~ e can be cal-
culated.
I t is fairly difficult to estimate of I , ( T ) and tt(T)
by some kinds of calculation, but it is not impossible.
By using several assumptions and h y p o t h e s i ~ , ~ ~ ' ~ - ~ ~ )
I , ( T ) and a ( T ) are roughly calculated as shown in
Fig. 1 lZ4) as a function of transformation tempera-
ture. I n this figure, I , shows a maximum value at
913 K (640°C) and n shows a maximum value at
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( 770 ) Transactions ISIJ, Vol. 27, 1987
873 K (600°C) fbr S15C steel (0.15 % C, 0.4 % Mn).
Figure l2Z4) shows a comparison of calculated
values and experimental values for C15C steel. Wc
can get a roughly agreement, that is, a-grain size is
getting smaller with cooling rate increases. The Sor-
mulations are :
Dtv = Q-0. 17(D, )1' ~cal ~ul at ~d) ... ......... ...... (23)
Do = 5.7Q-0.2'3(D,)0.46 (experimental) . . . . .. . . .(24)
Figure 1324) shows experimental results.
IV. Ferrite Grain Refinement by Work-harden-
ing of Austenite
I . Ferrite Nucleation in Deformed Austenite (Isothermal)
Figure 14 is typical micrographs showing the effect
of austenite defhrmation on the progress of ferrite
transformation.Z5) Specimens of an Fe-0.12C-0.04-
Nb-0.04V steel were austenitized at 1 200°C for 30
min, rolled 30 or 50 % in reduction by a single pass
at 840°C (in the unrecrystallized temperature range)
and held at 680°C for 15, 30 and 180 s. The ferrite
transformation is clearly accelerated by deformation
COOLI NG IRATE , K is
Fig. 1 l'erritc grain s i ~ e as a function of cooling rate lor
the specimens of D, = 15 1 pm. (S 15C) Fig. 13. Ferrite grain size as a function of Q-0.2'3Dt4G.
Not Rolled Rolled (30%) Rolled (50%)
(a) Non-deformed, 15 s (b) 30 % rolled, 15 s (c) 50 % rolled, 15 s
(d) Non-deformed, 30 s (e) 30 % rolled, 30 s (f) 50 % rolled, 30 s
(g) Non-defbrmed, 3 min (h) 30 % rolled, 3 min (i) 50 0/6 rolled, 3 min
Fig. 14. Optical micrograph showing the efrect of austenite deformation on the proccss of' ferrite transfbrma-
tion at 680°C in a Fe-O.12C-0.04Nb-0.04V steel.
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( 771 )
ofaustenite. I n the non-deformed specimen austenite
grain boundaries are the predominant nucleation sites
of ferrite, but in the deformed specimens nucleation
occurs not only on austenite grain boundaries but also
within grains. Moreover, the nucleation rate on
grain boundaries is substantially accelerated.
Figure 15 shows various types of nucleation sites of
ferrite observed in deformed specimens.25) Figure
15(a) shows ferrite grains nucleated at austenite grain
boundaries. The ferrite grains grow into both sidcs
of austenite grains, and the prior austenite grain
boundaries disappear once ferritcs are nucleated. Fig-
ure 15(b) shows the ferrite grains nucleated at the
annealing twin boundaries. In contrast to the non-
deformed specimens, the annealing twin boundaries
in the deformed specimens are the preferential nuclc-
ation site of ferrite. The ferrite grains nucleated at
annealing twin boundaries grow mostly into one side,
and the traces of prior annealing twin boundaries
remain after transformation. Figure 15(c) shows fer-
rite grains nucleated intragranularly. These ferrites
were considered to be nucleated on the dislocations at
the cell wall distributed almost uniformly inside the
grains. Figure 15(d) shows the ferrite grains nucle-
ated at decormation bands.
The increase in the ferrite nucleation rate per unit
volume of austenite by deformation is attributed (1)
to the increase in the austenite grain surface by elon-
gation of grains, (2) to the increase in the nucleation
rate per se per unit area of grain surface, and (3) to
the formation of additional nucleation site such as
annealing twin boundaries, deformation bands, etc.
The grain boundary surface area of austenite per
unit volume of a specimen increases by deformation.
A spherical austenite grain (Fig. 16(a)) becomes an
ellipsoid as shown in Fig. 16(b) by applying the roll-
ing with reduction p. The surface area of a grain
with an unit radius before rolling is given as
The surface area of the grain after rolling with reduc-
tion p is given as
S,.,,(p) = St''-* [(q x J: J 1 -(2p-pvsiFzB do.
-1'1-*
l h c ratio of the surface area before to after rolling,
q(=S,.b/SO,.,,), is plotted in Fig. 17 as a function of
rolling reduction p. Since the volume of the sphere
shown in Fig. 16(a) is equal to that of the ellipsoid
shown in Fig. 16(b), the ratio q in Fig. 17 is equal to
that obtaining to grain surface areas per unit volume
before and after rolling. I t is seen that the increase
in the grain surface area per unit volume with the in-
crease in p is quite small when p is smaller than 0.5.
For instance 50 % reduction by rolling increases the
surface area by 25 %. This increase is equivalent to
that obtained by only 20 0/, reduction in austenite
grain size.
The number of ferrite grains nucleated on austenite
grain boundaries is substantially increased by defor-
mation. Figure 1825) shows the ferrite grains nu-
cleated on the austenite grain boundaries: (a) non-
deformed, (b) 30 % rolled, and (c) 50 % rolled,
respectively. From these pictures the acceleration of
ferrite nucleation rate on austenite grain boundaries
by deformation can be estimated. The number of
ferrite grains intersect per 1 mm of austenite grain
(a) (b)
(a) Kcfore rolling (sphere)
(b) After rolling (ellipsoid)
l i g. 16. Tlic shapc change ol' an austcnite grain by the
rolling with reduction p.
Rolled (30V0) 30s Rol led(30%) 15s
(a) W~ ~ c . l t , ~ ~ t i o ~ ~ ;it gr~ii11 I>o~~n(laric~s
(I,)
Nuc.l(.atiun on ; i ~ni ~. nl i ~i g t \ \ . i r ~ I)ou~~cl ; i ri c~~
(c.) S~i cl cnt i on i n d c gr;iinr
((1) Suclc:~tion on clt.IL1.1nntion bantls
Fig. 15.
Opticxl n>ic.rogl.nplis showi~lg lllr \ . ; ~r i o ~~i types 01'
~iucleatiun bites 01' IC3rrite obier\,ccl i l l drll1.111rd
specimens. Rolled(50%) 15s Rolled(30%) 15s
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strain & (=-ln(1-p))
0 -0.5 - 1.0
1 7
--
1.6
--
1. 5
--
1.4
--
1.3
--
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Rolling Reduction p
Fig. 17. The ratio of austenitc grain surfacc arca bcforc
rolling to that of after rolling as a f~~nct i on of roll-
ing rcduction $.
boundaries werc counted as 4 1, 214 and 330 for
0, 30 and 50 rolled specimens, respectively. The
numbers of ferrite grains nucleated per unit area
of austenite grain boundary surface are proportional
to the square of these numbers. Furthermore the
number of ferrite grains nucleated per unit area of
austenite grain surface, n,, is proportional to the
square root of I, as is shown in Eq. (10). Since a is
not much changed by deformation, the ferrite nuclea-
tion rate per unit area of austenite grain boundary
surface is estimated to be increased by 740 ((214/41)4)
and 4 200 ((330/41)4) times faster by 30 and 50 %
rolling, respectively.
As is shown above, the nucleation of ferrite on
austenite grain boundaries is substantially accelerated
by deformation. The mechanism of enhanced nu-
cleation is considered to be as follows. The deformed
austenite grain boundaries may have many ledges (or
steps) shown schematically in Fig. 19(a). If ferrite
nucleates at the corner or such a ledge, as is shown
in Fig. 19(b), the activation energy for nucleation be-
comes B/n times less than that fbr nucleation on a
planar grain boundary (if the surface energy is as-
sumed to be equal for all kinds of interfaces). Thus
if a large number of ledges are produced on grain
boundaries by deformation, considerable increase in
the nucleation rate can be expected. As is shown
in Fig. 15(b) the annealing twin boundaries in
work-hardened austenite also act as the preferential
nucleation site of ferrite. The reason of this can be
considered to be as follows. At the coherent twin
boundaries before deformation a large number of
ledges are produced on the twin boundaries by
deformation. Thus deformed twin boundarics have
Not Rolled
680 'C
3min
Rolled (5O0Io)
680 O C
30s
(a)
Non-deformed, 3 min at G80°C
(b)
30 0/, rolled, 3 s at 680°C
(c)
30 % rolled, 3 s at 680°C
1 18. Optical micrographs showing the efycct of defor-
mation on the number of ferrite formed on auste-
nite grain boundaries.
$.,,.,j- rcrrite
,A-F
(a)
A ledgc on grain boundary
(b)
Ferrite nuclcation at a lcdgc
Fig. 19. Scllematic drawing showing ferrite nucleation at
a ledge on deformed austcnite grain boundaries.
the similar structure with that of austenite grain
boundary surfaces and act as the preferential nu-
cleation site of ferrite.
Similar mechanisms have bcen proposed for the
enhanced nucleation on deformed austenitc grain
boundaries by several researchcrs. Sandberg and
Robertsz7) have suggested that deformation leads to
the formation of grain boundary serrations or bulges,
and these act as nucleation sites. Amin and Pic-
keringZ8) proposcd that deformed austenitc grain
boundaries appear to exhibit greater lattice mismatch,
possibly because of greater lattice distortion and a
higher dislocation density near deformed grain bound-
aries. These would be the predominant nucleation
sites of ferrite and hence accelerate the nucleation.
Deformation structures within austenite grains have
bern known to act as the effective nucleation sites of
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( 773 )
ferrite and play an important role in the ferrite grain
refinement. The deformation structure is generally
called as deformation bands. These regions are char-
acterized by a high density of cells consisting of tangled
dislocations. Dislocations are favor nucleation sites
through its stress field. Consequently ferrite nuclea-
tion appears to occur frequently at the deformation
structures.
2. Growth of Ferrite in Deformed Austenite (Isothermal)
When ferrite grains grow into deformed austenite,
their growth rate would be accelerated by the follow-
ing two factors. One is due to the enhancement of
diffusivity by dislocations and supersaturated vacan-
cies. Another is due to the additional driving force
associated with stored energy. Since carbon, whose
diffusivity controlls the growth rate of ferrite in HSLA
steels, is an interstitial element, the former effect is
considered to be small. The latter [actor is also not
so large estimation by some kinds of calculation (ac-
celeration is less than 10 %).z4) We can find that the
ferrite growth rate is slightly enhanced by the defor-
mation of austenite. The acceleration of growth rate
by deformation is much less than enhancement of nu-
cleation rate for the transformation kinetics.
3. Ferrite Grain Size firmed ,from Dfirmed Austenite
(I~othermal)2~)
For simplicity we assume;
(i)
that austenite grain boundary surfaces are the
nucleation site and the additional nucleation sites
produced by deformation are the deformation bands
and annealing twin boundaries,
(ii)
that the nucleation rates per unit area of de-
formation bands and annealing twin boundaries are
equal to that of the grain boundary surface,
(iii)
that the total area of deformation bands and
annealing twin boundaries per unit volume of auste-
nite is quadratic with respect to
the strain E ( = -In (1 -P)), i.e.,
S,.,i(p)+Sl.l,(p) = A(- In (1 -p))2 ......... (27)
where, A is a constant, and
(iv)
that the ratio JI, (p)/ a(p) can be expressed
as a function of strain e as,
where, Io, a,: the nucleation rate and parabolic rate
constant of growth in the non-de-
formed specimen, respectively
B: a constant.
An exponent of 1.3 came from an experiment for Fig.
18.
As discussed above the ferrite grain size formed
from non-deformed austenite in the case of grain sur-
face nucleation can be expressed by Eq. (1 1). From
the assumptions made for deformed specimen Sg.b in
Eq. (1 1) should be replaced by the effective interfacial
area, S,, which is the sum of the areas ofgrain bound-
ary surface, annealing twin boundary and deforma-
tion bands ( S, ( P) =Sg . b ( p ) +Sd . ~( P) +St . h( P) ) . Fur-
thermore, if both the nucleation and the growth rates
are a function of strain, the ferrite grain size in the
deformed specimen is considered to be expressed as
Thus if d I o / wo and the coefficients A and B are de-
termined from an experiment, the ferrite grain size
formed from deformed austenite can be calculated.
Figure 20 shows an example of such calculation.
Here the calculated ferrite grain size using the com-
monly observed values of JIi/cuo, A and B is plotted
as a function of the rolling reduction, P. From this
figure it is seen that the ferrite grain size formed from
work-hardened austenite decreases drastically with the
increase in a rolling reduction for a small rolling re-
duction and decreases gradually for a large rolling
reduction.
4. Ferrite Grain Refinement by Accelerated Cooling
Accelerated cooling after hot rolling is currently
being realized as a further advanced thermomechani-
cal treatment in hot rolling proce~s.29>3~) This cooling
process is characterized by accelerated cooling in a
7-+a transformation range just after controlled rolling.
I t has been shown that the accelerated cooling refines
the ferrite grain size and thus further improves both
the strength and toughness.
The effect of accelerated cooling on ferrite grain
refinement can be seen in a non-deformed specimen.
Figure 13 and Eq. (24) show the effect of cooling rate
on ferrite grain size in an Fe-0.15C
This dependence of ferrite grain size by cooling
rate means that when a cooling rate becomes 10 times
faster ferrite grain diameter becomes almost half
(0.55).
The principle of grain size refinement by accel-
erated cooling can be understood by considering the
effect of transformation temperature on ferrite grain
size in an isothermal transformation. As mentioned
in the previous section the grain size of isothermally
formed ferrite depends on the ratio of the square root
Da(prn)lnDa True Strain & = -ln(l-p)
1.0 2.0
40
30.-
20-3 0 Austenite Grain Size
10..
2 .o
5-
1.0
0 .I .2 .3 .4 .5 .6 .7 .8
Rolling Reduction, p
Fig. 20. Calculated ferrite grain size formed from work-
hardened austenite as a function of rolling reduc-
tion for various austenite grain sizes.
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of nucleation rate to the parabolic rate constant for
various types of nucleation sites. Thus when the
ratio d n a increases with the decrease in the transfor-
mation temperature, the grain size of an isothermally
formed ferrite decreases with the decrease in the
transformation temperature.
The continuous cooling transformation can be con-
sidered as the sum of short time isothermal holdings
at successive temperatures, as described in previous
section and derived two equations of (21) and (22)
which show n, and D,, respectively.
As a whole, austenite deformation results in a large
increase in the ratio of the nucleation rate to the
parabolic rate constant and leads to ferrite grain re-
finement. The accelerated cooling further refines a
ferrite grain size.
V. Structures and Properties of Martensite
Formed f rom Work-hardened Austenite
I . Morfhology of Microstructure Composed of Lath Mar-
tensite Formed from Work-hardened Austenite
Among various types of ferrous martensite (such as
lath, lenticular, etc.) the lath martensite is the most
important one because most of the commercial heat-
treatable steels produce lath martensite. Lath mar-
tensite structure is characterized by packets and blocks
within a original austenite grains as shown schemati-
cally in Fig. Zl.31) It is known that the basic micro-
structural unit for controlling mechanical properties
especially, toughness of lath martensitic steel is size of
packets or bl o~ks, ~2-3~) and thus the refinement of
packets or blocks improves the mechanical properties
of lath martensitic structure. Therefore, we examined
the change in lath martensite morphology with the
amount of deformation of austenite using an 18 Ni
maraging steel (18.3 % Ni, 9.0 % Co, 5.0 % Mo, 0.7
% Ti, 0.015 % C) and Nb bearing low carbon steel
(0.12 % C, 0.038 % Nb, 0.039 % V).
An example of results in 18 Ni maraging steel is
shown in Fig. 22.35) In this case, specimens were
austenitized at 1 523 K for 120 s in Ar gas atmosphere
(austenite grain size of 200 pm was obtained by this
treatment) and cooled to 773 K (above M d tempera-
ture) and deformed in tension to various strains at
773 K at strain rate of 3 x 10-2/s and then air cooled
to room temperature to produce lath martensite. It
appears from Fig. 2233) that the number of packets in
an austenite grain markedly decreases and hence the
packet size becomes large with an increase in the
amount of deformation of austenite. The block be-
comes narrower and finely segmented, and the block
boundaries become heavily waved with an increase in
the amount of ausforming. Figure 23 shows the
change in the mean packet size and block width of
lath martensite in 18 Ni maraging steel with the
amount of ausforming. These results indicate that
the morphology of ausformed lath martensite is char-
acterized by large packet size and less-developed
blocks. And also it is characteristic that the block
boundaries are waved in the case of ausformed mar-
tensite. Similar tendency was observed in low carbon
Nb steel (HSLA steel) as shown in Fig. 24, in which
the specimen was rolled at 1 123 K by 50 % after
austenitizing at 1 573 K for 1.8 ks and then water
quenched to produce lath martensite. These micro-
structural characteristics might arise from the pre-
ferential formation of lath martensites with the same
habit plane along the most active slip plane (one of
four (11 11, planes) which is macroscopically bent by
heavy deformation.
As shown above, the packet size of ausformed mar-
tensite is large compared with that of conventionally
quenched lath martensite. I t was observed that the
ausformed lath martensites form along the curved
{111}, planes as shown in Fig. 22(f)35) and Fig. 24
(b).") This indicates that the crystal planes of aus-
tenite (and hence, of martensite) are bent. I n such
a situation, there would be a possibility that the
propagation of cleavage crack is suppressed since the
plane of cleavage fracture ({001],,) is heavily waved.
This might be one reason for some improvements in
toughness by ausforming in spite of the coarsening of
packet size.
2. Mechanical Proferties of Ausformed Martensite
In order to account for the good ductility of aus-
formed steels, the relation between the ductility of de-
formed austenite and the ductility of ausformed mar-
tensite was studied using an Fe-25.4XNi-0.38XC
alloy (Ms=236 K).37) I n this experiment, specimens
were solution treated at 1 423 K for 10.8 ks. Since
the M s temperature of this alloy is below room tem-
Fig. 2 1. Schematic illustration showing the morpholog-
I
0.2% Carbon Steel
I
ical characteristics of lath martensite structure
l8Ni Maraging Steel
in 0.2 0/, C steel and 18 % Ni maraging steel.
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( 775 )
( a ) ( c ) :
Packed structure (electrirally etched with CrO, 10 g+H, O 90 cc)
( d ) ) :
Block structure (chemically etched with FeCI, 10 g+HCl 30 cc+H, O 120 cc)
Fig. 22. Optical micrographs showing the change in packed or block structure of lath martensite with
amount of deformation oT austenite (ausformed by tennion at 773 K) in 18Ni maraging steel.
1
0 0.1 0.2 0.3 0.4 0.5 0.6
True Strain
Fig. 23. Change in the packet size and block width of lath
martensite with the amount of deformation of
austenite (ausformed at 773 K) in 18Ni maraging
steel. D, = 200 pm.
perature, the solution treated specimen was austenite
single phase at room temperature. These specimens
were deformed at 473 K by rolling to various amounts
of reduction. The rolling temperature of 473 K was
applied in order to avoid the formation or strain-
induced martensite during deformation. Some of
specimens of deformed austenite were subzero cooled
into liquid nitrogen to produce the ausformed mar-
tensite. Tensile properties were measured in both
specimens of deformed austenite and ausformed mar-
tensite with an Instron-type tensile machine at 353 K
(a)
1 573 K for 1.8 ks -+ W. Q.
(b)
1 573 K for 1.8 ks --t 50 % rolled at 1 123 K
-t w.9_.
Fig. 24. Optical micrographs of non-ausformed (a) and
ausformed (b) lath martensite in Nb steel.
Etchant: 2 % nital.
which is above Md temperature.
Figure 25 shows the results of tensile strength of the
deformed austenite and the ausformed martensite.
Both of tensile strengths of austenite and martensite
are increased with an increase in the amount of
prior-deformation of austenite. Figure 26 shows the
relation between the elongation and the amount of
prior-deformation of austenite. In the case of de-
formed austenite, the elongation is markedly decreased
(from 60 to 3 %) with an increase in the amount of
prior-derormation. On the other hand, it is charac-
teristic that the elongation of ausformed martensite is
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Test temperature: 353 K
P, T: Parallel and transverse specimens against
rolling direction, respectively
S: Subzero cooling to 77 K, namely speci-
mens are of martensite
Fig. 25. Relation between tensile strength and the amount
of prior-deformation of austenite at 473 K in
Fe-25Ni-0.38C alloy.
hardly effected by the amount of ausforming and is
almost same as the elongation of non-ausformed mar-
tensite. The ausformed martensite exhibits almost
constant elongation of about 8- 10 %, irrespective of
the amount of ausforming. Therefore, the elongation
of deformed austenite becomes smaller than that of
ausformed martensite, when the amount of deforma-
tion (ausforming) is more than about 30 % in the
case of the present alloy. I t must be emphasized that
the heavily deformed austenite is rather enhanced in
both strength and ductility by martensitic transforma-
tion.
These results indicates that the dislocations in
austenite produced by deformation are inherited and
that the stress concentrated region at the obstacles in
austenite produced by heavy deformation are healed
by the martensitic transformation itself. As a reason
for the healing effect, it can be considered that the
stress concentration in austenite may be released by
the formation of preferential variants of martensite at
the stress-concentrated areas.
3. Effect of Ausforming Temperatures on the Increase of
Strength ff Ausformed Martensite
I n the most published papers, the strength of aus-
0 15 30 L5 60
Pre-deformation ( % )
Test temperature: 353 K
Fig. 26. Relation between elongation and the amount of
prior-deformation of austenite at 473 K in Fe-
25Ni-0.38C alloy.
formed martensite has been studied mainly by func-
tions of the amount of deformation and the defor-
mation temperature below Al . And it is generally
believed that the increase in the strength of ausformed
martensite is closely related to the amount of work-
hardening of austenite. However, few attempts have
been made to relate the strength of ausformed mar-
tensite to the flow stress of austenite during ausform-
ing at elevated temperatures.
I n order to make clear this point, the experiment
was carried out using austenitic steels (a high Mn
steel : 13.9 % Mn, 0.68 % C) and Fe-high Ni alloy
(32.4 % Ni 0.005 % C), and martensitic steels (SNC
815: 3.0 % Ni, 0.8 % Cr, 0.16 % C).38) Ausforming
was performed with a tensile machine at various tem-
peratures between 773 and 1 173 K at strain rate
of 1 . 7 ~ 10-21s. After deformation, specimens were
rapidly quenched by water spray. These ausformed
specimens were tensile tested at room temperature at
strain rate of 1 . 7 ~ 10-3/s to measure the yield stress of
deformed austenite (austenitic steels) and ausformed
martensite (martensitic steels) at room temperature.
Figure 27 shows the relation between the increase
in 0.2 % proof stress at room temperature (Aa;.,) of
ausformed austenite and the amount of work-harden-
ing (Aar) of austenite by ausforming at elevated tem-
peratures in austenitic steels. It appears that the
yield stress increase of austenite (Aa;.,) at room tem-
perature is linearly proportional to the amount of
work-hardening of austenite (Aur) by ausforming in
both steels, and all data lie on the same straight line,
irrespective of ausforming conditions such as defor-
mation temperature and the amount of strain. This
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(777)
result indicates that the strength of ausformed austen-
ite at room temperature is uniquely determined only
by the amount of work-hardening by ausforming.
This probably suggests that the strengths of austenite
at both of high and room temperatures are mainly
determined by the dislocation density.
Figure 28 shows the relation between the increase
of 0.2 % proof stress of ausformed martensite (Au;:~)
(i.e., the difference of 0.2 % proof stress at room tem-
perature between ausformed martensite and conven-
tionally quenched martensite) and the amount of
work-hardening (Aar) in austenite at elevated tem-
perature in SNC 815 steel. It is characteristic that
the obtained data lie on the different curves by the
ausforming temperature. It should be emphasized
that the d a f , is not determined only by the Aar, but
functions of both Aar and ausforming temperature.
Even at the same Aar, the effect of ausforming on the
strengthening of martensite is different with the de-
at H.T.
E
Fig. 27. Relation between the increase in 0.2 O//o proof
stress at room temperature of ausformed austenite
(do:,) and the amount of work-hardening of
austenite (Aor) by ausforming in austenitic steels.
formation temperature, i.e., do;:, is increased with an
increase in deformation temperature. Furthermore,
when the ausforming temperature is fixed, the con-
tribution of A 0 7 on the An;:, is small at smaller Aur
range and becomes large at larger Aar range. Same
tendency was also observed in SKD 61 steel. These
results strongly suggest that, in addition to the dislo-
cation density in austenite, the dislocation configu-
ration in austenite is also an important factor for
increase in strength of ausformed martensite.
Figure 29 shows the examples of transmission elec-
tron micrographs of austenite in a high Mn austenitic
steel deformed to the same amount of work-hardening
(Aor= I0 kg/mm2) at different temperatures. As can
be seen, the total dislocation density seems to be
almost same, but the dislocation configuration is dif-
ferent from each other. With increase in the defor-
mation temperature, the dislocation configuration is
changed from uniformly distributed pile-up to disloca-
tion cells. I n this austenitic steel, despite the dif-
ference of dislocation configuration the 0.2 % proof
Deformat ion temperature:
30
- A -993K
-1023K
25. o -1073K
L1
E
E 0
b 2 0 -
Y 0
e
rT 15-
C
0
- N
0
Q 0
5 .
0 5 10 15 20
bar at H.T. kg.rnrn-=
Fig. 28. Relation between the increase in 0.2 % proof
stress of ausformed martensite (dot,;) and the
amount of work-hardening of austenite (do?) by
ausforming in SNC 813 steel (3Ni-0.8Cr-0.16C).
Fig. 29. Transmission electron micrographs of austenite deformed to the same amount of work-hardening of
austenite ( Au~= 10 kg/mm2) at strain rate of 1.7 x 10-2/s at (a) 1 073 K, (b) 1 023 K and (c) 873 K,
respectively, in Fe-14Mn-0.7C austenitic steel.
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stress of austenite at room temperature is the same as
shown in Fig. 27, because the Aar is the same. How-
ever, as shown in Fig. 28, in the case of ausformed
martensite, Aa$, is increased as the ausforming tem-
perature is raised even at the same Aor. Therefore,
it can be considered that the dislocation cell structure
in prior austenite is very effective in strengthening of
ausformed martensite through the martensitic trans-
formation, and pile-up or uniformly distributed dis-
locations in prior austenite have little effect on
strengthening of ausformed martensite.
VI. Hardenability of Work-hardened Austenite
and Recrystallized Austenite
As described in the former section, the work-hard-
ened austenite can transform easily by diffusional
process, because the rate of nucleation of ferrite is
high. It means that the hardenability of steel is de-
creased with work-hardening of the austenite.
A bearing steel (SUJ2: 1.33 % Cr, 0.9 % C) with
spheroidized carbide particles was austenitized at
850°C at which the steel was in two phase region of
y and carbide, and deformed by compression of 60 %
(s=3x 10°/s), and then immediately or after holding
in some intervals of time (At) at the same temperature
as the deformation quenched into water. The hard-
ness at the center portion of SUJ2 specimen at room
temperature after quenching changed with holding
time (At) as shown in Fig. 30.
The austenite of SUJ2 with spheroidized carbide
particles can dynamically recrystallized easier than
without carbide particles. The work-hardened aus-
tenite of SUJ2 has poor hardenability and becomes its
hardenability recover to usual SUJ2 with holding
time (At) during the static recrystallization is progress-
ing as shown in Fig. 30.
Ausforming is quenching method of work-hardened
austenite. Such an austenite has poor hardenability.
The steel for ausforming should have high harden-
ability by including several alloying elements of Ni,
Cr, Mo, etc.
For direct quenching it seems that the austenite is
deformed and recrystallized and then quenched. In
this case, we can not expect to increase strength and
toughness of martensite as ausforming does.
I I I I W.Q.
6001 100 1
200 300 400
~t Hold~ng Time ( 5 )
Fig. 30. Change in hardness of water-quenched specimen
with holding time after deformation at 850°C in
SU.J2.
VII. Conclusion
I have explained the abstract of kinetics, structure
and mechanical properties of transformation products
of ferrite and martensite formed from work-hardened
austenite. Because of too much contents, I am afraid
that it would be difficult to understand.
Thank you very much for your kind attention.
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M. Umemoto, N. Komatsubara and I. Tamura: Proc.
Int. Conf. Solid-Solid Phase Transf., ed. by H. I. Aaronson
el al., TMS-AIME, Pittsburgh, (1981), 11 11.
M. Umemoto, H. Ohtsuka and I. Tamura: Proc. Int.
Conf. High Strength Low Alloy Steels, ed. by D. P. Dunn
and T. Chandra, Univ. Wollongong, Wollongong, (1984), 96.
G. H. Gulliver: J. Inst. Met.,19 (1981), 145.
J. R. Bradley, J. M. Risbee and H. I. Aaronson: Metall.
Trans. A., 8A (1977), 323.
M. Umemoto, Z. H. Guo and I. Tamura: Proc. Int. Conf.
HSLA Steels (HSLA Steels, Metallurgy and application^,
HSLA Steel '85), ed. by J. M. Gray et al., ASM-INTER-
NATIONAL, Beijing, (1985), 97.
C. Zener: J. Appl. Phys., 20 (1949), 950.
M. Hillert and L. I. Staffanson: Acta Chem. Scand., 24
(1970), 3618.
H. I. Aaronson and H. A. Domian: Trans. AIME, 236
(1966), 781.
C. Wells, W. Batz and R. F. Mehl: Trans. AIME, 188
(1950), 553.
L. Kaufman, S. V. Radcliffe and M. Cohen: Decomposi-
tion of Austenite by Diffusional Process, ed. by V. E.
Zackay and H. I. Aaronson, Interscience Publisher, a divi-
sion of John Wiley & Sons, N. Y., (1962), 313.
C. Wagner: Trans. AIME, 194 (1952), 91.
W. F. Lange and H. I. Aarowon: Metall. Tranc., in press
(Private communication).
M. Hillert: Lecture on the Theory of Phase Transforma-
tion, ed. by H. I. Aaronson, TMS-AIME, Pittsburgh
(1975), 1-50.
C. A. Dube: PhD Thesis, to Carnegie Institute of Tech-
nology, (1948).
M. Umemoto, Z. H. Guo and I. Tamura: Muter. Sci.
Technol., 3 (1987), 249.
Special Lecture
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Menu
Transactions ISIJ, Vol. 27, 1987
( 779 )
25) M. Umemoto, H. Ohtsuka, H. Kato and I. Tamura:
Proc. Int. Conf. High Strength Low Alloy Steels, ed. by
D. P. Dunn and T. Chandra, Univ. Wollongong, Wol-
longong, (1984), 107.
26) M. Umemoto, H. Ohtsuka and I. Tamura: Trans. Iron
Steel Inst. Jpn., 23 (1983), 775.
27) A. Sandberg and W. Roberts: Proc. Int. Conf. Thermo-
mechanical Processing of Microalloyed Austenite, ed. by
A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981), 405.
28)
R. K. Amin and F. B. Pickering: Proc. Int. Conf. Thermo-
mechanical Processing of Microalloyed Austenite, ed. by
A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981), 377.
29)
C. Ouchi, J. Tanaka, I. Kozasu and K. Tsukada: " Op-
timization of Processing, Properties and Service Performance
through Microstructural Control ", ASTM Spec. Tech.
Publ. No. 672, (1979), 105.
30)
H. Sekine, T. Maruyama, H. Kageyama and Y. Kawa-
shima: Proc. Int. Conf. Thermomechanical Processing of
Microalloyed Austenite, ed. by A. J. DeArdo et al., TMS-
AIME, Pittsburgh, (1981), 141.
31)
T. Maki, K. Tsuzaki and I. Tamura: Trans. Iron Steel Znst.
Jpn., 20 (1980), 207.
32) S. Matsuda, T. Inoue, H. Miura and Y. Okamoto:
Proc. of Int. Symp. on Toward Improved Ductility and
Toughness, ISIJ and JIM, Tokyo, Sendai, (1971), 47.
33) Y. Ohmori, H. Ohtani and T. Kunitake: Met . Sci., 8
(1974), 357.
34) A. R. Marder and G. Krauss: Proc. of Int. Conf. Strength
of Metals and Alloys (Znd), 111, ASM, Asilomar, (1970),
822.
3.5) I. Tamura, K. Tsuzaki and T. Maki: Proc. of Int.
Conf. Martensitic Transformation (ICOMAT-82), ed. by
L. Delaey et al., Les Edition de Physique, Paris, Leuven,
(1982), c4-551.
36)
I. Tamura, T. Maki and H. T. Yui: to be published.
37)
Y. Tomota, K. Tanabe, K. Kuroki and I. Tamura:
J.
J p n Inst. Met., 41 (1977), 313.
38)
C. K. Yao, S. Y. Gao, T. Maki and I. Tamura: Proc.
3rd Int. Cong. Heat Treatment of Materials, ed. by T.
Bell, Metals Soc., London, Shanghai, (1983), 5-80.
Special Lecture
Menu
Journal of Applied Sciences Research, 2(8): 484-485, 2006
© 2006, INSInet Publication
Corresponding Author:
2
O.E. Olorunniwo, Department of Material Sciences and Engineering,
Obafemi Awolowo University, Ile-ife. Osun state, nigeria
484
Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment
1
J.A. Omotoyinbo,
2
O.E. Olorunniwo,
2
O. Ogundare and
2
O.O. Oluwole
1
Federal University of Technology, Akure. Nigeria.
2
Obafemi Awolowo University, Ile-Ife. Nigeria.
Abstract: Micro-alloyed steels produced by controlled rolling are of the most attractive propositions in many
engineering applications because of their relative low cost, moderate strength and very good toughness when
compared withas-cast alloy steel.. This research work has shownthe possible substitution of cheaper, low-alloy
steel for the highalloy steel for the same application. The effect of HTMT onthe mechanical properties of low
alloy steel was investigated.
Key words: Strengthening. High Temperature Themomechanical Treatment (HTMT), micro alloyed,
controlled rolling.
INTRODUCTION
Steels are weaker than they should be theoretically
because of dislocations and the ease with which these
dislocations moveunder applied shear stress
[4]
. Therefore,
the primary aim of strengthening is to retard the
dislocationmovements. However, complete barrier canbe
dangerous because pile-up of dislocations can lead to a
catastrophic crack
[2]
.
Strength in steels arises from several phenomenon
including solid solution strengthening, dispersion
strengthening and ferrite grain refinement which usually
contribute collectively to the observed mechanical
properties such as ductility, strength,etc. Alloying
elements’ presence provides greater control over
microstructure and consequent benefit in mechanical
properties.
Therefore, to produce steels with improved
strength-to-ductility ratio, a combined use of mechanical
working and heat treatment is employed as
strengthening mechanism
[8]
, resulting in structural steels
withimproved weldability, cleannessand inclusionshape
control
[9]
.
This paper seeks to investigate and establish the
possible benefits derived from strengthening of alloy
steels by HTMT. This includes improved mechanical
properties, substant ial energy savings (through
elimination of subsequent normalizing treatment) and
possible substitution of cheaper, low alloy steel for high
alloyed steel for the same application under the same
conditions.
Experimental procedure: The chemical composition of
low alloy steel as-cast specimens (AISI-SAE 1037),
presented in table 1, was obtained from the Universal
Steels Limited, Lagos, Nigeria. All mechanical tests
(tensile, hardness, impact) were carried out according to
the A 296 ASTM requirement.
MATERIALS AND METHODS
Tensile test samples: To prepare the tensile test
specimen, the hot-rolled samples which were initially of
round shape were prepared as follows. The 10mm
diameter rod was held tightly in position on the bench
vice where it was cut into lengths of 5mmach with he aid
of hack saw. Each of the samples was then mounted and
turned consecutivelyon the lathe machineinto cylindrical
shape. The vernier caliper was used to take the accurate
measurement. For reproducibility of results, four samples
were prepared for the 10mm diameter rod. This process
was repeated for the 12mm and 16mmdiameter rod, one
after the other.
The impact test samples: They were prepared by
notching to 4mm depth at 45
0
with the aid of the lathe
machine. Four samples were prepared each for 10mm,
12mm and 16mm diameter rod as well as for the as-cast
sample to be used in izod impact test.
The hardness test sample-This sample is obtained by
grindingthe surface with emery paper. Then, withthe aid
of hacksaw and lathe machine, cut into 25mm x 25mm x
25mmsquare cube for Rockwell test. Four samples were
prepared for 12mm and 16m diameter samples.
Microstructural test: The specimens were ground in
successionwith220,320, 400, 600frit emerypaper. Then,
they were polished until mirror-like surfaces was
obtained. The surface was etched withNital solution and
examined under the microscope. For reproducibility of
results, four samples were prepared for 10mm, 12mmand
16mm samples.
RESULTS AND DISCUSSIONS
From the result, it has been shown that the rolled
(HTMT) samples possess both the yield strength and the
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J. Appl. Sci. Res., 2(8): 484-485, 2006
485
1 2 3 4
97.99%
Deformation
98.87%
Deformation
92.22%
Deformation
AS.CAST
60
50
40
30
20
10
0
B
r
i
n
e
l
l
h
a
r
d
n
e
s
s
v
a
l
u
e
s
60
50
40
30
20
10
0
1 2 3 4
AS.CAST
97.99%
Deformation
98.87%
Deformation
99.22%
Deformation
I
m
p
a
c
t
v
a
l
u
e
s
(
j
o
u
l
e
s
)
`% red. Fracture UTS Yield strength Hardness Impact
Sample % Elongation in area strength N/mm
2
N/mm
2
N/mm
2
HRC (J)
10mm diam as- rolled 1.80 51.41 668.11 688.78 255.10 47.58 48.15
-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
12mm diam. As –rolled 4.63 56.55 367.36 377.55 239.8 41.4 45.57
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
16mm diam as-rolled 7.81 61.26 213.64 221.94 147.96 37.45 41.40
--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
As-cast 0.80 3.60 171.94 - - 55.78 11.25
Table 1: The low alloy steel specimens used have the following
composition in weight percent as below.
C 0.368 Sn 0.014
Si 0.226 Al 0.003
S 0.33 Zn 0.003
P 0.039 Mo 0.021
Mn 0/688 Cu 0.227
Ni 0.177 As 0.014
Cr 0.119 Co 0.013
V 0.002 Pb 0.001
W 0.003 Fe 98.055
Fig. 1: Average hardness values.
Fig. 2: Impact values
Ultimate Tensile Strength while the as-cast samples do
not. Reasons that could be adduced to these are that,
during the HTMT, the as-cast sample has its defective
structure homogenized, blowholes and gas pores welded
shut and atomic segregation reducedand internal stresses
relieved
[3]
. These, coupled with hot plastic deformation
as well as the presence of alloying elements (carbide
formers such as nickel, titanium, etc), inhibiting
dislocation movement, to effect strengthening with
respect to Ultimate Tensile Strength (UTS) and yield
stress
[2,9]
.
Also, the as rolled (HTMT) samples are much more
ductile than the as cast samples for the same reason cited
above
[6]
. Conversely, the as-cast samples are harder than
the as rolled due to the presence of inclusions, residual
internal stress, residual coring and non-uniformity during
solidification, which are virtually elimination by
HTMT
[1,8]
.
Conclusion: The application of HTMTon low alloysteel
has led to the reductionin hardnesswhile the strength and
toughnessincrease considerably, compared to the as-cast
samples. Hence, for applications that require adequate
me chani cal pr oper t i es, hi gh t emp er at ur e
themomechanically treated low alloy steel should be
employed
REFERENCES
1. Adeyeye Oluseyi, 1996. Influence of thermo
mechanical working on the strengthening of
Aluminum alloys, Unpublished B.Sc. Thesis,
Metallurgical and Material Engineering department,
Federal University of Technology Akure, Nigeria,
1998
2. Benjamin, W.N., B.D. Alan, and A.W. Richard,
1989. Modern manufacturing process Engineering
McGrawHill, NewYork, pp: .32-33, 61-62 , 77-114.
3. Bolton, 1988. Production Technology-Processes,
Materials and planning Heinemann London pp:
174-185.
4. Dieter, G.E. 1988 Mechanical metallurgy McGraw
Hill, London, pp: 309-312.
5. Degarmo, E.P., J.T. Black and A.K. Ronald, 1993.
Materials and processes in manufacturing, 7th Edn.
Macmillan, London, pp: 222-223.
6. Higgins, R.A., 1993. Engineering Metallurgy part 1:
Applied Physical Metallurgy’ 6th Ed. 124: 219-233,
285-330.
7. Llewellyn, D.T., 1992. Steels: metallurgy and
application’ 1st Edn., Butterworth Heinemann,
oxford, pp: 64-77.
8. Rajan, T.V, C.P. Sharma and A. Sharma, 1988. Heat
treatment-principle and techniques, McGraw Hill,
India, pp: 175-181.
9. Novikov, L., 1978. Theory of Heat treatment of
metals,’ 1st Edn. Moscow, pp: 105-106, 418-425.
10. Honeycombe, RWK, 1981. Microstructure and
properties’ 1st Ed., Edward Arnold, London, pp:
167-185.
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High Performance Copper-Precipitation-Hardened Steel

Semyon Vaynman, Morris E. Fine
Department of Materials Science and Engineering and Infrastructure Technology Institute
Northwestern University
Evanston, IL 60208

Riad I. Asfahani
U.S. Steel Research and Technology Center
4000 Tech Center Drive
Monroeville, PA 15146

David M. Bormet
U.S. Steel Plate Products
Gary Works
One North Broadway
Gary, IN 46402

Christopher Hahin
Illinois Department of Transportation
Bureau of Materials and Physical Research
126 E. Ash Street
Springfield, IL 62704



Introduction

This paper presents data for a high performance hot-rolled
and air-cooled low-carbon, copper-precipitation-hardened steel
developed at Northwestern University (NUCu steel). The
approach taken for developing a tough, strong, improved
weldability and weatherability steel
1-4
was to derive additional
strength by copper precipitation hardening which occurs during
air cooling. Further increase in strength is achieved by aging
after air cooling or normalizing. Nickel is present to prevent hot-
shortness during hot rolling but also gives solid solution
strengthening. Niobium was added to reduce grain size. The
steel has very low carbon equivalent weldability index.
The initial development was done with laboratory heats of
steel that were produced at Inland Steel Company and US Steel
Research and Technology Center. Two commercial 80,000-kg
heats were produced at Oregon Steel Mills (OSM) to investigate
the steel production under industrial conditions and for bridge
repair. These heats were cast into slabs by a bottom pour
process. Results of the previous work were published earlier
1-4
.
Recently a slab previously cast at OSM was hot-rolled at
U.S.Steel Gary Works. The production and properties of plates
made from this slab are presented and discussed in this paper.

Experiments

The cast steel slab, 178-mm (7-inch-) thick, received from
OSM was cut in two and hot-rolled into plates of 25.4-mm (1
inch) and 19.1 mm (0.75-inch) thickness. The cast slabs were
reheated to 1066
o
C (1950
o
F) and then rolled. The first pass for
the 25.4-mm-(1-inch-) thick plate was done after the slab was
cooled down to 973
o
C (1783
o
F). The finishing hot-rolling
temperature for this plate was 937
o
C (1719
o
F). The second slab
was first rolled down to 96.3 mm (3.79-inches) and then it was
reheated to 1277
o
C(2300
o
F). Before rolling was continued the
slab was cooled to 1039
o
C (1902
o
F) and then rolled down to
19.1 mm (0.75 inches). The finishing rolling temperature for this
plate was 937
o
C (1719
o
F), the same as for the 25.4-mm- (1-inch)
thick plate. The plates were air cooled after hot rolling. Portions
of the plates were cut for specimen preparation. Some of these
were austenitized at 900
o
C(1650
o
F) and air-cooled or quenched.
The time at temperature for austenitizing and/or aging was 40
minutes per inch thickness.
Round tensile specimens with a gauge section of 50.8 mm
(2 inches) (ASTM E8 Standard) and Charpy specimens (ASTM
E23 Standard) were machined in longitudinal direction from the
quarter thickness of the plates and tested. For each plate multiple
specimens were tested with very little variation observed. A
metallographic study was also made.
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Results and Discussion

Chemical Composition. Chemical composition of the steel
heat is shown in the Table 1.
Mechanical Properties. Results of the mechanical testing
are summarized in the Tables 2-5. Tables 2 and 3 demonstrate
the effects of different treatments on mechanical and fracture
properties respectively of the 19.1-mm- (0.75-inch)-thick plate.
As-rolled the yield stress is 503 MPa (73 Ksi) and 567 MPa (82
Ksi) ultimate tensile strength. The elongation exceeds 30%. The
Charpy absorbed impact energy is remarkably high down to
–40°C (-40°F), the lowest temperature used. Previously we
found
2-4
that the Charpy absorbed impact energy is reduced
significantly if the rolling temperature exceeded 1150°C
(2100°F). This was attributed to the formation of Widmanstatten
ferrite at high temperatures. Despite the fact that the second
reheat temperature for the slab used to roll this plate was
1277
o
C(2300
o
F) cooling the slab down to 1039
o
C (1902
o
F)
before continuing the rolling gave 161J (118 ft-lb) Charpy
absorbed impact energy at -40°C (-40°F). Microstructural
examination did not find any Widmanstatten ferrite present in
the steel.
Aging of as-rolled 19.1-mm- (0.75-inch)-thick plate
increased the strength of the steel by about 35-45 MPa (5-7 Ksi)
with only a very slight reduction in the Charpy absorbed impact
energy. Normalizing reduced the strength, but significantly
increased the Charpy absorbed impact energy. Aging of the
normalized steel significantly increased the strength with some
reduction of the Charpy absorbed impact energy. Quenching and
then aging of the steel had a significant effect on the properties.
The yield strength increased dramatically when the steel was
quenched from 900°C (1650°F) and then aged at 524°C (975°F)
but the Charpy impact energy was reduced to 64 J (47 ft -lb) at
-40°C (-40°F), still a high value for a structural steel at this low
temperature. Increasing the aging temperature reduced the yield
strength to about 650 Mpa (95 Ksi) but increased the Charpy
impact energy.

Table 1. Composition of the steel (wt.%)

C Mn P S Si Cu Cr Mo Nb Al Ca
0.06 0.78 0.006 0.005 0.38 1.37 0.06 0.03 0.038 0.029 0.0037


Table 2. Mechanical properties of 19.1 mm (0.75 inch)-thick plate


Plate Condition
Yield Strength*
MPa (Ksi)
Tensile Strength
(Ksi)
Elongation (%) Reduction in
Area (%)
As-Rolled and air cooled 503 (73) 567 (82) 32.2 68.7
As-Rolled & Aged 524
o
C (975
o
F) 539 (78) 610 (89) 33.0 64.6
Normalized 900
o
C (1650
o
F) 461 (67) 546 (79) 36.2 63.1
Normalized & Aged 524
o
C (975
o
F) 557(81) 638 (93) 35.2 66.5
RhQ& Aged 524
o
C (975
o
F) 712 (103) 780 (113) 26.3 62.5
RhQ& Aged 552
o
C (1025
o
F) 658 (96) 733 (107) 29.8 65.2
RhQ& Aged 579
o
C (1075
o
F) 642(93) 716 (104) 29.5 68.0
* 0.2% offset.

Table 3. Charpy absorbed impact energy of 19.1-mm (0.75-inch)-thick plate

Charpy - V- Notch Impact
Energy, J (ft –lbs) at temperatures:

Plate Condition

-40°C (-40°F)

-23°C (-10°F)

-12°C (+10°F)

0°C ( +32°F)
As-Rolled and air cooled 161 (118) 192 (141) 202 (148) 206 (151)
As-Rolled & Aged 524
o
C (975
o
F) 149 (109) 164 (120) 173 (127) 179 (131)
Normalized 900
o
C (1650
o
F) 233 (171) 242 (177) 255 (187) 257 (188)
Normalized & Aged 524
o
C (975
o
F) 126 (92) 153 (112) 165 (121) 176 (129)
RhQ& T 524
o
C (975
o
F) 64 (47) 89 (65) 115 (84) 132 (97)
RhQ& T 552
o
C (1025
o
F) 124 (91) 143 (105) 152 (111) 169 (124)
RhQ& T 579
o
C (1075
o
F) 168 (123) 175 (128) 183 (134) 214 (157)

Results for the 25.4-mm (1-inch)-thick plate, Tables 4
and 5, are similar to those for the 19.1-mm- (0.75-inch)-thick
plate. As expected, the strength of 25.4-mm (1-inch)-thick plate
is slightly lower. Since copper precipitation is the main
strengthening mechanism, slower cooling in a thicker plate leads
to larger copper precipitates.
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The microstructures are very similar in both steel plates and
are functions of heat-treatment. The microstructures of the 25.4-
mm (1-inch)-thick plate are shown in Figure 1. The steel has an
equaxed ferritic microstructure. In as-rolled, as-rolled and aged,
normalized, and normalized and aged conditions pearlite regions
are observed. They form bands parallel to the surface of the
plates. Pearlite is not present in the quenched and aged steel.
While the average grain size is approximately 12-15µm in the
as-rolled steel, the grains in quenched and aged steel are
significantly smaller, on the order of a few microns. Reduction
in grain size contributes to the strength of the steel in addition to
strengthening from copper precipitate aging. Copper precipitates
could not be observed in optical microscope, they are
approximately 3 nm in diameter as determined in the three
dimensional atom probe
5
.


Table 4. Mechanical properties of 25.4-mm (1-inch)-thick plate


Plate Condition
Yield Strength*
MPa (Ksi)
Tensile Strength
(Ksi)
Elongation (%) Reduction in
Area (%)
As-Rolled and air cooled 465 (68) 547 (80) 32 70
As-Rolled & Aged 524
o
C (975
o
F) 625 (91) 665 (97) 26 61
Normalized 900
o
C (1650
o
F) 466 (68) 542 (79) 36 72
Normalized & Aged 524
o
C (975
o
F) 559 (81) 636 (92) 31 72
RhQ& T 524
o
C (975
o
F) 678 (99) 756 (110) 29 68
RhQ& T 552
o
C (1025
o
F) 661(96) 737 (107) 28 67
RhQ& T 579
o
C (1075
o
F) 615 (89) 682 (99) 29 73
* 0.2% offset.

Table 5. Charpy absorbed impact energy of 25.4-mm (1-inch)-thick plate

Charpy - V- Notch Impact
Energy, J (ft –lb) at temperatures:

Plate Condition

-40°C (-40°F)

-23°C (-10°F)

-12°C (+10°F)

0°C ( +32°F)
As-Rolled and air cooled 161 (118) 187 (137) 221 (162) 228 (167)
As-Rolled & Aged 524
o
C (975
o
F) 64 (47) 117 (86) 132 (97) 150 (110)
Normalized 900
o
C (1650
o
F) 205 (150) 266 (195) 258 (189) 270 (198)
Normalized & Aged 524
o
C (975
o
F) 137 (100) 164 (120) 173 (127) 195 (143)
RhQ& T 524
o
C (975
o
F) 96 (70) 124 (91) 167 (122) 202 (148)
RhQ& T 552
o
C (1025
o
F) 98 (72) 106 (78) 160 (117) 173 (127)
RhQ& T 579
o
C (1075
o
F) 195 (143) 238 (174) 235 (172) 238 (174)

Welding. Due to the very low carbon level and the absence
of chromium and molybdenum NUCu steel has a very low
carbon equivalent welding criterion. The steel was designed to
be welded without pre-heat or post-heat. Previously welding was
evaluated without pre-heat or post-heat by a submerged arc
(SAW) process and also by a manual process in a construction
shop environment (Trinity Bridge and Arlington Construction
Companies). Matching consumables were used. No brittle heat-
affected zone was formed. These results were confirmed in a
welding laboratory at Northwestern University using very high-
energy input
2-4
.
Duplicate G-BOP tests conducted earlier at the U.S. Steel
Research and Technology Center using a heat input of 1.4
KJ/mm (53 KJ/inch) and low hydrogen AWS E7018 and E9018
electrodes without pre-heat or post-heat did not show weld metal
cracks in the welds or base plates.
Stupp Bridge Company, Bowling Green, Kentucky, recently
performed a Procedure Qualification (PQR) SAW Test without
pre-heat and post-heat using Lincoln LA85 electrodes and
Mil800-HPNi flux. The heat input was 2.36 KJ/mm (60
KJ/inch). In fracture tests; at -30°C(-22°F) the average Charpy
absorbed impact energy was 124 J (91 ft-lb). The requirement by
American Welding Society Standard is 34 J (25 ft-lb) at this
temperature.
Corrosion Performance. Copper imparts weathering
resistance in inland and marine environments and the high
copper content in NUCu steel is effective in substantially
reducing the weight loss in accelerated weathering tests.
In SAE J2334 standard accelerated tests performed at
Bethlehem Steel Corporation by Townsend
7
, the weight loss of
NUCu steel was compared to that for A36 steel and other
weathering steels. Townsend’s results are summarized in Figure
2. The thickness loss of A36 steel was133% greater than that of
NUCu steel. The thickness losses of A588 weathering steels and
HPS70W A709 steel were 69% larger than that of NUCu steel.
Using existing data bases corrosion indexes have been
established and the index for NUCu steel is far lower than that
for any other structural steel
6,7,8
.
At the present time NUCu steel together with a number of
plain carbon and weathering steels are being exposed at different
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As-Rolled

As-Rolled & Aged 524
o
C (975
o
F)

Normalized 900
o
C (1650
o
F)

Normalized & Aged 524
o
C (975
o
F)

RhQ & T 524
o
C (975
o
F)

RhQ & T 552
o
C (1025
o
F)

RhQ & T 579
o
C (1075
o
F)
Figure 1. Microstructure of 25.4 mm- (1-inch-) thick plate
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corrosion sites around the USA to establish the long time
weathering resistance but not enough time has elapsed to reach
any firm conclusions
7
.
The same steel grades were coated with epoxy -based
Carboguard 890 paint from Carboline Company, scratched and
then tested in a salt -fog chamber (ASTM B-117 Standard, 49.97
g/liter salt solution). The extent of corrosion was measured after
exposure at 35
o
C for 3 weeks. Results of the tests are shown in
the Figure 3. The widths of the corroded regions adjacent to the
scratches are compared to the weight loss reported by Townsend
in Fig. 4. Again NUCu steel showed the best corrosion
resistance; the corroded surfaces at the scratches of A36, A588
and HPS 70W A709 steels were 93%, 52% and 54%
respectively wider than that of NUCu steel.
Figure 2. Results of the accelerated corrosion test (automotive
SAE J2334 Standard) performed at Bethlehem Steel Company
7


Figure 3. Painted steel panels after 3 weeks, 35
o
c exposure in
salt-fog chamber (A36; A588; ASTM HPS70W; NUCu (ASTM
A710 Grade B) steels)


Acknowledgments

Support of Northwestern University’s Infrastructure
Technology Institute is appreciated.



Figure 4. Comparison of the width of the rusted region on the
salt sprayed scratched painted steel panels with the thickness
loss of the bare steel panels in SAE J2334 tests.

Summary

Copper precipitation strengthening is an alternate route to
quench and tempering or thermomechanical processing to a high
performance low-carbon 70-grade structural steel. Cast slabs of
a NUCu steel 200 mm thick were hot-rolled to 25 and 19 mm
thickness and air-cooled. Tensile and Charpy impact tests were
done on samples as cooled, aged, normalized, and normalized
and aged. With the 25.4-mm- (1-inch-) thick plate aging after air
cooling from hot rolling or normalizing was required to reach
the desired yield strength level. Particularly noteworthy are the
very high Charpy impact energies at cryogenic temperatures.
The 19-mm- (0.75-inch-) thick plate successfully passed a PQR
welding test without pre-heat or post-heat and with matched
welding rods. Corrosion tests on bare and painted panels are
reported. The corrosion for NUCu steel was significantly less
than that for ordinary weathering steels including the high
performance A709W steel.

References

1. M.E. Fine, R. Ramanathan, S. Vaynman, S.P. Bhat,
International Symposium on Low Carbon Steels for 90's,
p. 511, ASM International , Cincinnati, OH (1993)
2. S. Vaynman, M.E. Fine, G. Ghosh, S.P. Bhat, Materials for
the New Millennium, Proceedings of the Fourth Materials
Engineering Conference, p. 1551, ASCE, New York, New
York (1996)
3. S. Vaynman, I. Uslander, M.E. Fine, Proceedings of 39th
Mechanical Working and Steel Processing Conference, p.
1183, ISS, Indianapolis, Indiana (1997)
4. S. Vaynman, M.E. Fine, International Symposium on Steel
for Fabricated Structures, p. 59, ASM International ,
Cincinnati, OH (1999)
5. M. Gagliano, D. Isheim, unpublished research
6. S. Vaynman, R.S. Guico, M.E. Fine, S.J. Manganello, Metall.
Trans., 28A, 1274-1276 (1997)
7. H. Townsend, retired from Bethlehem Steel Company,
private communications
0
100
200
300
400
500
600
A36 A588B HPS 70W NUCu
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r
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o
s
i
o
n

L
o
s
s
,

m
i
c
r
o
n
s
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1
2
3
4
0 200 400 600
Thickness Loss, microns
W
i
d
t
h

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f

t
h
e

R
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s
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e
d

S
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r
a
t
c
h
,

m
m
NUCu
A709 HPS70
A588
A36
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Comprehensive Characterization of Ageing
Behaviour in M250 Maraging Steel using
Multi-NDE Techniques


K.V. RAJKUMAR, ANISH KUMAR, T. JAYAKUMAR, S. VAIDYANATHAN,
S. MAHADEVAN, B. SASI, G. AMARENDRA,
Metallurgy and Materials Group,
Indira Gandhi Centre for Atomic Research, Kalpakkam, India,
BALDEV RAJ AND K. K. RAY
Indian Institute of Technology, Kharagpur, India


Abstract: Nondestructive measurements have been carried out in M250 grade
maraging steel specimens subjected to solution annealing at 1093 K for 1 h followed
by ageing at 755 K for various durations in the range of 0.25 to 100 h. Different NDE
techniques such as ultrasonic velocity, magnetic barkhausen emission (MBE), positron
annihilation spectroscopy (PAS), eddy current and X-ray diffraction (XRD) have been
employed for comprehensive characterization of microstructural features evolved
consequent to aging treatment.


1.0 Introduction

M250 grade maraging steel, by virtue of its excellent mechanical properties i.e. ultra-high
yield strength combined with good fracture toughness [1], is the preferred structural material
for critical applications in advanced technologies. In addition to the above mentioned
properties, its high strength to weight ratio, good weldability and easy machinability in the
solution annealed condition and dimensional stability during aging make this material as an
ideal choice for critical rocket motor casing applications in aerospace industries. The ageing
behaviour of the maraging steels has been extensively studied [2-12]. The strength in aged
condition is derived from the fine and coherent intermetallic precipitates, whereas low carbon
martensitic structure provides the high fracture toughness. Over-aging results in coarsening of
the intermetallic precipitates in addition to the reversion of martensite to austenite. These two
processes that occur due to overaging affects both tensile and fracture properties of these
steels. Hence, characterization of microstructure plays an important role in qualification of
fabricated components for service. Particularly, non destructive evaluation (NDE) techniques
are most sought as they provide fast and reliable means of characterizing microstructures of
actual components.
Various NDE techniques such as ultrasonic, magnetic Barkhausen emission (MBE),
positron annihilation spectroscopy, X-ray diffraction and eddy current testing have shown
good promise in characterizing the microstructure in various alloy systems. Though
considerable work has been done on other alloy systems, so far no systematic study has been
carried out for characterization of aging behaviour in maraging steels, which leads to
complex microstructure consequent to aging. In view of this, in the present study, an attempt
has been made to unfold the effects of various microstructural features of maraging steel that
evolve during aging treatment, on different NDE parameters and in-turn to develop
ECNDT 2006 - Fr.1.7.1
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nondestructive methodology for comprehensive assessment of ageing behavior of M250
grade maraging steel.

2.0 Experimental

The chemical composition (wt %) of the maraging (M250) steel used in this study is as
follows: 17.89 Ni, 8.16 Co, 4.88 Mo, 0.43 Ti, 0.05 Mn, 0.05 Cr, 0.05 Si, 0.05 Cu, 0.096 Al,
0.003 C, Bal. Fe. A plate of maraging steel (M250) was solution annealed at 1093 K for 1 h
followed by air cooling. The specimens of approximate dimensions 30x25x7 mm extracted
from the solution annealed plates, were encapsulated in quartz tubes under vacuum and aged
at 755 K for different durations of 0.25, 1, 3, 10, 30, 40, 70 and 100 h followed by water
quenching. The same sets of specimens were used for all the NDE studies using multiple
techniques. The Vicker’s hardness measurements were carried out on the specimens at 10 kg
load. The average value of five hardness measurements has been reported for each specimen.
The maximum scatter in the hardness measurements was found to be less than ± 5 VHN.
For ultrasonic measurements, surface grinding of the heat treated specimens was
carried out to obtain a constant thickness of 7 mm and plane parallelism to an accuracy of
better than ± 2 μm. Ultrasonic velocity was measured at room temperature using 15 MHz
longitudinal wave and 5 MHz shear wave transducers. A 100 MHz broad band pulser-
receiver (M/s. Accutron, USA) and 500 MHz digitizing oscilloscope (M/s. Lecroy, USA)
were used for carrying out the ultrasonic measurements. Cross correlation technique has been
used for precise velocity measurements [13]. For the velocity measurements, the ultrasonic
signals were digitized at 500 MHz and the gated backwall echoes from the oscilloscope were
transferred to a personal computer with the help of GPIB interface and specific software
developed in LabVIEW. The accuracy in time of flight measurements was better than 1 ns
and the maximum scatter in the ultrasonic velocity was found to be less than ± 2.5 m/s.
Magnetic Barkhausen emission measurements were performed using encircling pick
up coil (5000 turns) and magnetizing the sample at a frequency of 66 mHz. A U-shaped
electromagnet assembly was used to magnetize the maraging steel specimen
(30mmx25mmx7mm) fixed between two conical pole pieces of an electromagnet. The
maximum field was set to 1500 Oes for complete magnetic saturation of the specimen. This
corresponds to a magnetization field strength (H) of 80 0000 A m
-1
. The MBE signal was
amplified using a low noise preamplifier and a post amplifier (80 dB). The detailed
experimental setup for MBE measurements has been reported elsewhere [14].

XRD measurements were carried out using MAC Science MXP18 X-ray
diffractometer with Cr K
α
radiation and the samples were analyzed in the complete angular
range of 60-130°. The volume percent of austenite formed by reversion of martensite during
ageing, was determined by direct comparison of the integrated intensities of the (111) and
(200) planes of the γ phase with the intensities of the (110) and (200) planes of α phase.
Positron Doppler broadening measurements were carried out using a high purity
germanium detector having an energy resolution of 1.4 keV at annihilation gamma ray energy
of 511 keV. A defect sensitive line shape S-parameter viz. the ratio of central peak counts to
total counts around 511 keV γ-ray is deduced from these measurements. The S-parameter
signifies the positron annihilation events with low momentum electrons of the medium.
Various defects such as vacancies, vacancy clusters, dislocations and precipitate–matrix
interfaces act as trapping sites for positrons, leading to an increase in the S-parameter value
[15].
The eddy current (EC) testing was carried out using MIZ-20A ZETEC system with
optimized testing parameters such as frequency (10 kHz) and phase (5°). Specially designed
probe consisting of transmit-receive (T/R) coil was used, which was relatively insensitive to
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permeability variations. The EC response is measured in terms of signal amplitude i.e.
magnitude of real and imaginary components.

3.0 Results and Discussion

Figure 1 shows the variations in hardness, ultrasonic longitudinal wave velocity and positron
annihilation parameter (S parameter) with aging duration. The variation in the ultrasonic
velocity with aging time exhibits similar trends as that of the hardness. The velocity initially
increases with aging time, peaked at intermediate ageing duration followed by continuous
decrease at longer durations of ageing. In contrast, the S parameter decreased drastically from
the solution annealed conditioned up to 1 h of aging and then increases with further aging.
Figure 2 show the variations in hardness, MBE rms voltage, volume % of austenite
and EC amplitude value with aging duration. The variation in the EC amplitude with aging
time exhibits similar trends as that of the volume of austenite determined from XRD. They
were initially constant and increased drastically at longer aging time. In contrast, the MBE
rms value remained constant initially and drastically dropped at longer aging durations.





















Fig. 1. Variation in hardness, ultrasonic wave velocity and
Positron Annihilation (S Parameter) with aging at 755 K.

The initial increase in the hardness up to 3 h is attributed to the precipitation of Ni
3
Ti
intermetallic precipitates from the martensite matrix. The detailed transmission electron
microscopy (TEM) results substantiating this have been reported elsewhere [16]. The
continuous increase in the hardness at intermediate durations (10-40 h) is attributed to
additional precipitation of fine Fe
2
Mo precipitates from the solid solution. The decrease in the
hardness upon ageing for longer durations is attributed to the formation of soft reverted
austenite phase. The variation in ultrasonic velocity with aging exhibited similar behaviour
as that of hardness. The initial increase in the ultrasonic velocity is attributed to the
precipitation of mainly Ni
3
Ti intermetallic phase, which increases the hardness up to 616
VHN. The subsequent steep rise in velocity reaching a maximum is attributed to the
precipitation of Fe
2
Mo along with Ni
3
Ti. The variation in ultrasonic longitudinal wave
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Hardness
S Parameter
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velocity and hardness with ageing time could reveal various stages of precipitation and
reversion of austenite; however the initiation of the reversion of austenite at 30 h of ageing
could not be identified by ultrasonic velocity measurements. Though TEM studies revealed
the initiation of reversion of austenite occurring below 30 h itself [16], decrease in hardness
and ultrasonic longitudinal wave velocity is observed only after 40 h of ageing. This is
attributed to the fact that the precipitation of Fe
2
Mo, which tends to increase the hardness and
velocities, continues to take place in parallel with the austenite reversion. Hence, decrease in
the hardness and ultrasonic longitudinal wave velocity due to formation of austenite can be
felt only when this decrease is more than the increase in these parameters due to continued
Fe
2
Mo precipitation. Drastic drop in velocity at longer aging duration is attributed to the
formation of reverted austenite. Austenite has been reported to be a soft phase having lowest
modulus among all the phases present in ferritic steels [17].
Unlike hardness and ultrasonic velocity, S parameter drastically decreases upon
ageing up to 1 h duration and increases continuously beyond this up to 100 h of ageing
(Figure 1). The initial decrease in S parameter up to 1 h of ageing is attributed to annihilation
of defects and reduction in defect density associated with precipitation. The main defects
observed in these steels are vacancies and dislocations. Reduction in the defect density with
aging occurs especially during the initial aging time, when defect density is the highest.
Hence, the decrease in the S-parameter in the initial regime (up to 1h) of aging is attributed to
two simultaneous mechanism i.e. the reduction in defect density due to martensitic recovery
and predominantly the precipitation of intermetallics preferentially on defects, which results
in decrease in trapping sites. On the other hand, coarsening of precipitates acts as trapping
sites due to the strain field associated with them, leading to the increase in the S parameter.
Since the two processes affect the S parameter in opposite ways, net effect is manifested as
continuous decrease up to 1 h showing the reduction in defect structure as the dominant
feature beyond this the precipitation is found to be the dominant factor. Though at longer
ageing durations (30-100 h), reversal of austenitic also take place, the S parameter seems to
have subtle affect as it results in only structural change with less effect on defect
concentration. The continuous increase in S parameter up to 100 h is the result of continuous
precipitation of intermetallics, which acts as trapping sites for positrons.
Figure 2 shows the variation in EC amplitude with aging time for M250 maraging
steel. EC amplitude remained almost constant up to 10 h of aging. Aging for 30 h resulted in
drastic increase in EC response compared to 10 h. The EC amplitude continued to increase
with further aging for longer durations reaching a value of 2.0 V at 100 h. Because of the
specially designed probe, the effect of permeability is nullified and the change in EC
response can be explained in terms of change in conductivity only. Though the EC amplitude
remained constant with aging time up to 10 h, the hardness increases continuously in this
regime due to precipitation of intermetallics. From this it can be inferred that the change in
resistivity is negligible with precipitation of Ni
3
Ti initially and Fe
2
Mo at later stage. Upon
ageing for 30 h, the EC amplitude increased drastically due to the presence of austenite in the
microstructure. From the TEM investigations [16], it was also evident that austenite is
observed earliest in the specimen aged for 30 h. Habiby et al. [18] have also reported similar
observations in similar steel upon ageing. Even a very low volume fraction of austenite (less
than 1% in specimen aged for 30 h) could be easily revealed because of the substantial
difference in the resistivity values for martensite and austenite. The resistivity values for pure
iron and stainless steel differ widely i.e. 2463x10
-7
ohm-m and 7.496x10
-7
ohm-m
respectively. The eddy current parameter could be correlated with the amount of reverted
austenite and hence has potential for in-situ detection and assessment for austenitic reversal
on actual components.

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Fig. 2. Variation in hardness, magnetic barkhausen emission RMS,
Eddy current RMS value and Volume % of austenite
determined by XRD with aging at 755 K.


Figure 2 also shows the variation in MBE peak height and volume % of reverted
austenite (measured by XRD) with ageing duration for the isothermally aged specimens at
753 K. The MBE peak height remains almost constant up to 10 h of aging. Beyond this,
substantial drop in MBE rms voltage was observed on aging up to 100 h.
MBE rms voltage remains almost constant up to 10 h regime showing that the
increase in MBE rms voltage due to dislocation annihilation is compensated by decrease in
MBE rms due to precipitation of intermetallic phases. Hence, a net manifestation of constant
voltage is obtained. Beyond 10 h of ageing, the substantial decrease in MBE rms is attributed
to the formation of reverted austenite due to dissolution of Ni rich precipitates. An interesting
observation is that the onset of austenitic reversion is picked up sensitively by MBE whereas
it requires appreciable amount to be detected by XRD (~2% at 40 h). Otherwise early
detection of this austenite reversion requires support of TEM. The increase in austenite from
30 h to 100 h is evident from XRD. From Fig. 2, it is also evident that upon 40 h, 70 h and
100 h of ageing, the volume of austenite increases continuously as 2, 6 and 30 %
respectively. The substantial decrease in MBE with reversal of austenite is attributed to the
fact that the paramagnetic austenite impedes domain wall movement in addition to reducing
the total domains taking part in magnetization. This clearly indicates that the MBE technique
is very sensitive to characterize the initiation of austenitic reversion.
Ultrasonic velocity showed good promise in characterizing the intermetallic
precipitation process and was able to pick up the austenite information only when high
amount of austenite is precipitated. Its drawback is with respect to obtaining any information
about the defect structure and early detection of initiation of austenite reversion. Hence, this
technique is found to be very sensitive to monitor the intermetallic precipitation behaviour.
Positron annihilation studies were found to be very sensitive to defect structure and
precipitation to some extent. The austenite reversion has almost no effect on positron
annihilation parameter. Hence this technique can be used for high sensitive characterization
of defects such as vacancies or dislocations. Magnetic Barkhausen emission study showed
good promise in identifying the non-magnetic austenite phase compared to intermetallic
0.1 1 10 100
350
400
450
500
550
600
650
0
2
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%

o
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a
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f
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R
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M
B
E
,
R
M
S

V
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a
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d
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s
s
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V
H
N
Aging time, h
MBE RMS Voltage
EC Amplitude
Vol% austenite from XRD
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precipitation and defect structure. Hence, MBE technique can be used selectively for very
sensitive determination of early initiation of reversion of austenitic phase. Eddy current
technique is also found to have good promise in early detection of initiation and
characterization of the austenitic reversion ahead of ultrasonic and almost on par with MBE.
As this technique is more amenable to shop floor, it can be used for determination of volume
% of austenite in actual components with ease. XRD technique was found to be good in
characterizing austenite but was unable to determine the austenitic initiation early due to low
sensitiveness of the technique for austenite volume fraction (less than 2 %). Hence XRD
technique can not be used for recognition of austenite initiation and moreover its portability
to shop floor and to component site is difficult. However, XRD technique can be used as a
benchmark for establishing correlations for quantitative estimation of volume fraction of
reverted austenite using MBE and ECT techniques.

4.0 Conclusion

Various NDE techniques have been used in the present study for comprehensive
characterization of microstructural features generated by ageing the solution annealed M250
maraging steel at 755 K for different durations in range of 0.25-100 h. Each technique
provided complimentary information with regard to complex microstructural features that
evolve during the aging treatment of maraging steel. Ultrasonic velocity was found to be
more sensitive to the precipitation of intermetallics, whereas magnetic Barkhausen emission
could clearly identify the onset of austenitic reversion. Positron annihilation spectroscopy
could clearly identify the reduction in defect structure during initial aging periods, in addition
to the characterization of continued precipitation of intermetallics at longer aging periods.
XRD studies were used for quantitative determination of amount of reverted austenite. Eddy
current parameters could be correlated with the amount of reverted austenite and has potential
for in-situ assessment for austenitic reversion on actual components. The present study has
clearly brought out the complementary nature of various NDE techniques for comprehensive
characterization of ageing behaviour in maraging steels


ACKNOWLEDGEMENTS

We are thankful to Dr. S. L Mannan, Former Director, Metallurgy and Materials Group and
Mr. P. Kalyanasundaram, Associate Director, Inspection and Technology Group, Indira
Gandhi Centre for Atomic Research (IGCAR), Kalpakkam for their cooperation and support.
We are also thankful to Dr. B.P.C. Rao and Dr. C. Babu Rao of IGCAR, Kalpakkam for
useful discussions. We are also thankful to Dr. R. Rajaraman and Mrs. Padma Gopalan of
IGCAR, Kalpakkam for their support in carrying out positron annihilation studies.

5.0 References

1) G.P. Miller and W.I.Mitchell, J. Iron Steel Inst., 203, (1965) 899.
2) D.T. Peters and C.R. Cupp, Trans. Met. Soc. AIME, 236, (1966) 1420.
3) V.K. Vasudevan, S.J. Kim And C.M. Wayman, 1990, Metall. Trans. A 21, 2655.
4) W. Sha, A. Cerezo and G.D.W. Smith, Metall. Trans. A 24 (1993) 1221.
5) S. Floreen, R.F. Decker, in: R.F. Decker (Ed.), Source Book on Maraging Steels, ASM,
Metals Park, OH, 1979, pp. 20–32.
6) R.F. Decker, S. Floreen, IN: R.K. Wilson (Ed.), Maraging Steels: Recent Developments
and Applications, TMS-AIME, Warrendale, PA, (1988) pp. 1–38.
7) U.K. Viswanathan, G.K. Dey and M.K. Asundi, Metall. Trans. A 21 (1990) 2429.
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8) W. Sha, A. Cerezo and G.D.W. Smith, Metall. Trans. A 24 (1993) 1221.
9) W. Sha, A. Cerezo and G.D.W. Smith, Metall. Trans. A 24 (1993) 1233.
10) W. Sha, A. Cerezo and G.D.W. Smith, Metall. Trans. A 24 (1993) 1241.
11) W. Sha, A. Cerezo and G.D.W. Smith, Metall. Trans. A 24 (1993) 1251.
12) Z. Guo, W. Sha and D. Vaumousse, Acta Mater. 51 (2003) 101.
13) Anish Kumar, T. Jayakumar, Baldev Raj and K. K. Ray, Mat. Sci. & Engg. A, 360
(2003) 58.
14) V. Moorthy, S. Vaidyanathan, T. Jayakumar and Baldev Raj, Mater. Sci. Tech. 13 (7)
(1997) 614.
15) B. Somieski, R. Krause-Rehberg, H. Salz and Meyendorf, Journal DE Physique III, 5 ,
Janvier (1995).
16) K.V. Rajkumar, Anish Kumar, T. Jayakumar, Baldev Raj and K. K. Ray, “Characterization
of Aging Behaviour in M250 Grade Maraging Steel using Ultrasonic Measurements”,
Metall.& Mater.Trans A, Communicated (2006)
17) H.M.Ledbetter and M.W. Austin, Materials Science and Engineering, 72 (1985) 65.
18) F.Habiby,T.N Siddique, S.H.Khan, A Ul Haq and A.Q.Khan, NDT&E International
25, No.3, (1992) 145.

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Effect of Aging on Microstructure and Mechanical Property
of 1900 MPa Grade Maraging Stainless Steel
Kai L111'~*~, Yiyin SH/I,VI, Zhi.yonp YAN@), ~ianxiong LIANG'), Lun Lv) and Ke YANG1)q
3.1 Institute of Metal Eewarch, .Chinme Academy d Sciences, Shcnpg 110016, China
2) Graduate %ml or Chinwe At demy d Sciencw, B~ijing 100039, China
3) Gmerab Resewrh Institnke h r Iron md Steel, Beijing ID0081, China
41 Technical C~r r t ~r , D~ngbci Sp~cial St cd Croup Co,, Ashun lI3001, Chinh
[h.lanuaeript r m i d March 2, 20176, i n revised form Ortoher 16,
The 1S%Ni alfoy st& provide high strength and toughness, while agehardenable or PH stainfess st ei s also
have good corrosion resisance. This paper f o c u ~ on an investigation of the heat treatment, mechanical
propeei s and microstructural development of a new mayaging stainless; st el , I t is reported that the heat
treatment process should consist of solution treatment and cryogenic cooling to attain a fufly rnartensitic
structure, f o l l d by aghg a t 813 K. This heat treatment resulted in an ultimate tensile strength of owr
1900 MPa cornbi nd with good impact toughnes. Transmission electron microscopy is used t o show that.
for the peak-aged condition (813 K/4 h), nano-sized precipitates, e.g. Ni3Mo and/or R-phase, and a high
density of dislocations wete uniformly dispersed i n the lath martensite matrix. The calculatd yiclrl strength,
bawd an a revixd Orowan mechanism, is i n good agreement with the test data. The steel studied has an
ultimate tensile stwngth aver 1900 MPa, mcellent fracture toughness, and good mistance against over-aging
and relatively good cario5ion resishnct as well.
WORDS: Maraging stainless steals; Precipitati~n; High strength s t e l a ; Aging kmtment
Precipitation hardrning (PHI maraqing stainless
stwl is a spmi al dam of ul trahi gh atrrngth and
gmd tmaghnms rnart ~ns i t ~ stccl, which is also stain-
less, i . r, co~ttdns mow tl~rtn 11% [al l in wt pct)
~ r [ ' - ~ l . A p p mt l y , time, st wl s are suitable f i r r nwy
r n a i a ~ and pct mhmni cal applications, particnlnrly
where ch8orirEm are present. In general, PH stain-
less steel is solution treated at whole msteni ti c r e
@on for r proper time to homogar~i7~: chemical cam-
position, and then qucnchml to r r w m t a n p r a t u w to
ol>t;ljn a whole rnartc~~sitic microstructure '-4. Some
times, subzero temperature treatment, i . ~ . cryogwiic
treatment (CT), is a1.w applird after solution t r ~ a b
men1 (ST) becau~: d the 9tlh~ero rnartmsi ti c finish-
ing hmperatuw ( ~ f ~ ' r ] [ ~ - ' l . Finally, PR steel is & at
673-873 Ti fnr suitable time t o hrnl fins prptlipitates,
rcuch as Ni g31~, Fr2Mcl, and R ph~se, in a martcn-
site matrix, which cnabh PH stmf to reach its high-
est strength level and dm k e q good tolqhn%dln Is]-
Obviously, besidcs the important ml a of ST, &&
nf aging t r mt m~nt [AT] dm pla.m a very irnprtant
role an the mi ~ r o s t . r u ~ t u l ~ and machxnical p r n p ~ r t i r ~ ,
which have bml i nmt i gad by many reewclms. So
fa, di ffewnt conciusion,ns have heen drawn for diflcrent
maraging steels, and mur-h mfarch has also brrn d ~ -
voted t o deternuning t h ~ seructurm, precipitate t y p ~
a d rnechanicd propmties of BII sml s or marag-
i ng sttxls [IG-'!, such as the 18Ni ma rag in^ st wl s
and UITS 315500 maragingst;tinless steel;1'*L8.L9.24~251.
Hsiacs rt id,['" di scussd the aging reactions in UNS
517400 BH sldnlesrr s t e l at F2U-753 K for t.irnes
ranging froin 0.5 to R 11. T h ~ y anaiped the pre-
cipitate types md confirmed that 775 3 f~l r 1 h wafi
rmf,, Ph.D-, l o whom carnfiporrdmre shor~lrl he Rddmsd,
Fh-tail: kyangP%mr.Ar,ch.
the optimal adng t r ~ ~ t me n t . PTe d a1.M dcwl-
opd a new type of high stmgth maraging steel
by modification of the alloy campcwition, hut the
steel r c qui r d CT at 200 K in odc r t o obtain a
frlLly martensite matri x hared on dilatomttry ms~rlL5.
Vi swmathan el al.lal] studied the rnmhaniml prop-
erties, microstructure and precipitate typcs obtai n4
in C350 maraging steel duri q aging and mraging.
After aging at 783 K fm 3 h, t.he yield strcngth (a,)
xnb ultimatc tmsi l a stmgth. In,) mhi& t h ~ i r r n m-
imurn r;alue of 2195 5 d 2227 MPa, mpectiv~l)r, but
the impact encrgy (12 .I) and elongation (5.3%) wcm
quite low. I t is often difficult t o opt i r ni 7~ t he heat
twatmcnt paramPtmb, espwi dl y those for aging, so
as to ensure the highest stre~igth wl ~i l e maintaining
relatidy good duct iliby.
Up ta now, several PH stainbss steels are mmmer-
cially available, inc[uding UKS SI77130, LPJS S155WO
and XNS 545500. The age t~ardening of t hew allays i s
the: result, of alloyin# witti one or more of the! dements
Cu, Ti, Ma, Nb and A]. Generally speaking, the max-
imum tensile strength d~ve10pe.d in any d f h m dloys
is on the nrdar of lGDO m a . Hmevcr, mcept for t h e
new wire alloy, Bidine IRKSI, reported by Nilsson
et ~d. 1~~1 ultrahigh strength maraging stainlee4 sml
has not yet b e n reported.
hn thc prmcnt study, the Qarmtwistics d x new
type of ul trahi gh strength maraging stainlm &el are
examined. The composition of this s t ~ E was hasod
on pmi pi t at i ons of Mo phases in an FeCr - CeNi
marmsitr matrix. As a new typc d steel, the m-
dmmdi ng of the miwtmctlmral feature¶ t hat en-
aurc thc mmllcnt combinations of pprp~rties for this
steel are nut p t d ~ ~ r . Therefore, the purpme of the
pr mnt work W;L~ tT) wtimize the .aging pwmetprs
of Lhe stml , miifinn the pr w. i pi t at ~ &Tcc,t and under-
stand the nature of the dislocation-precipita~ inter-
action at rliffcrcnt stages of tile aging process. I t is
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belicwd that the infnrmatim drwl npd in this pa-
per will b wry m~~ni ngfl rl a d useful Em the further
dewioprnmt of a co~n~n~lrciaIl y uwf~il mat~rial.
The experimental &el waq pw@ by wc-
uum inrluctian meltin# and vacuum arc remelting
[VIM/VAR), and the rrr~minal chmi cd mrnpn~ir~ion
rangc is as follows I%): C [0.01-4.fl3), Cr (15.0-16.5),
Si (6.&7.5), Slo (6.6-7.51, Co (9.5-ll.@, S (<O.Ol),
P (<0.01), O [<O.Nl2), I4 [SD.OM), Fe @a].). A 50 kg
ingot was forgedl rolled bb~twwn a stclrting tmnpcrii-
turn o€ 1425 K and n finishing wmpcrature of 1123 K,
and the rmulting 20 mm rods wcw air cfir~!cd. Sam-
p!m nf the mrl WTY? dut i oi l treated at 1323 K Em. 1 h,
and rapid!y air coded to rrmm tmperarure. Th q
wr e t h ~ n cryogmimlly treatmi at 2211 0 for 8 h to
attain a Fully mwknaitic; matrix. Finall>*, t.hc ssm-
plcs ~mt l aged at 713, 763, $13 a~l d 873 K for a% long
as 20 h to mdym the qq+l~arrleni~lg c~lrve. Then,
Vi c h s h ~ l r d n ~ s twts wrc carricrl out in all condi-
t-ions. Staidarc1 tcnsih tests (samp!c dimctcr 5 mm)
were cxrriwl a~t on a tlG-;EDDIlA >ITS rnwliine at Qi s
placement rate of 0.2 m Jenin. Impact toughness was
t mt d r~singstmdard Gharpy U notch spcrjm~ns on a
REP 450 impact test, niashine. TI), spwi111rn3 wrr!
mted for each mndiLion anrl the data were a~~r agwi .
All tmts wcrc conducted at i mm txmperatur~.
DiIatomctric t i was pcrfomd otl. a
Fomzlrter-F diJatamed~r from Fuji Industry, lnc. For
this tcsling, s p ~ l mms cut, from tlw cqopnirrally
treated mrls wrc n~whi nd to 3 rnm diameter by
10 mtn long cylindrical mds wit11 a 2 mm r l i amar
and 2 rnm d e p hole in crnc side. During tire t ~ t ,
R wcurlrn of IU-' Pa w ~ 9 maintain4 l o yrot.ect the
sprimens Frnrn oxidation, and the length, time and
t cmpat ur e were fiimulL~ncously rcsor(l~1.
For t.rmmission ~lcctron rr~icrmctyq, t-hin foils
Wprr made from aged material, 0.3 ntm thick discs,
wcre mwhairidly p6Iish~d to 0.05 rnm thickn~ss
and t h n twin-jct c!lec?.rn-polished at 44 V i n a 92:R
[vol. pd) ethmnl: pcrchloric acid ~111t i on at 243 5.
'She solution rrcatd qxcirnms uere spmidly twatml
where lheY wr.r ion mil[Pd in order to keep the K+
taincd nusknire. All t h ~ thin bils sarnpl~s wew ex-
amin~d in a JEM 2011) transmission elclctron mi c m
s c o p ~ (Tl3hi) at ml arati ng wl tag~ nf 2.00 kV. Frrcc-
tographic examinxt~on of the iinpact-trrtml samples
wm rrwdrlctrd in a J3J3-58[XILY scanning cIcct,ron mi-
crawopo (SEM) b mduata the failure mode. X-ray
diffraction (XR.D) andysis was pwfnrmd in s ~ l mt ~ d
pond ition$.
3. Results
3,J Plme t~msfoma2ion
P11ase trmdtrmatinn tempwiltures during lthc rn-
Circ h ~ a t I r mt m~r ~t pmcws nvre estimat~d using
dilatometry. Figr~w I sttows t h ~ rlilaton~~try cirrvc
with thc various ttmsformation tempmiturn irldt-
catt.6. During hratjng, the Lwrw a n bc con$i d~r ~d ro
be n~ml y linear rlp t o 839 K. The point at wfiieh thc
CURT deviatd Dom Iin~arity iq identifier1 as t.11~ pw-
cipiLtirw st ari hg brnpcratzire, P,. I I ~ me r , P, was
much 11ighcr than that report4 in lit,~ratnm [7,19],
~ q i b l y rlnc to tile 11s~ of a faqter heating race in the
prment t.t%s, whir,^ pm?.poncd thc p~r.ipitatjon r e
action; and due to thc addition or Mo, bcxau~ MO
mntaining precipitatm am IikeTy tta farm al higlicr
t . mperat um and Iongm qi ng limes thm Ti con-
taining or Cu i,rt.r.ipitatn~[".L".191. A,, thc allstmite
da~t. ing tpmperdure, 835 X, and Af, the auetenik?
finishing tmpcraturr, 11 23 K, are dm d ~ s i g mt d in
Fig. 1 biiwd on deviations f m linearity in khc heating
t:onrp. Th~sc%i cdl y~ 1,hc t mt d stwl shr~uld bc W ~ U -
tion treated at a rrlativ~lp low w~npcratilre that is
abme Af, in order to avoitl the rapid grmtth of p,rdn
sixa that will rwtllt in the deceme in both s t r me h and
tonghnmsk41. Howmr , the ST tcmpwaturc, 1323 K,
was det.~rmind rrcmrding to rr ~ p t ~ m i c H.11dy d ST
prior ai ~st ~i i i t c gai n [PAG] siw and mechanical
pmpcrg of tesccd alloy, which was di scused in a sw
;irate paper. The main eonclraion drawn is that PAG
s i 7 ~ , af t ~r 57' for 1 h at 1323 K or l owr t ~mperat ut ~s
RW almmt the s mo , wdi i ng in minor jnfl~aencp on
mwhanic J property, Rut high ST tempmnt.llre is fa-
vurahlc to diasolvc alloying chmmts, e.g. Cr and hh,
i n lliE matrix and benrficial to harnn@nou~l distribu-
tion af yr~cipitates i nm the matrix in the foilawing
aging p~acms. )ME, the Mf i n s i t . ~ starting t~rnpcr-
at - ur ~, clhtaincd from the cooling c u m, was 353 K.
TEie martenbitre transformation m-as incornplelt~ aAm
amling to room Wmp~xatnrr-, ~n ,in,-if, thc martmensite
finishing fxmperatnnre, of the steel -4 shown to he
bdour room ternpel-atrlrrt. According tn t h ~ I;M,-Mf]
i.cl.rnpPlt.atrlm of other similar high alloy ~ t wl ~ ; ~ ~ ~ ' ] , the
Ms to ttmperat.ore rangc iis about 140 150 K. Con-
wqumt.ly it WM predict4 ?hat thc ,WE of the! t s t d
alhy shntlld ho appnximately 213 #, and -as also
dftermined by X3r;n.D phase analysis and TEM mmi-
nation of specimen CT, a4 will be disctlsserl latter.
3.2 3 f d i ~ i ~ P J property
Figrm 2 shows the prccipitaiim hIvdming clirvcs
of t h ~ t ~ t d steel a@ at 713, 763, 815 arrd 87.7 K,
wsp~tively. Oi Vi 0~4y, abt testid aginpimpwaturcs,
t h ~ bardn~ss i ncr~me rate wag quitr high mithin &Ire
'beginning 30 rnin of aging. Ewn aged at 713 K for
30 nlin, the hxrdnms d s pwi rr~~n r ~~whr d 425 Hhr.
Frorn thrn on, the inmasc In h;udnss was r~'lati.vdg
slow at 1nw a g i n ~ t.~~ruperaturw, i . ~ . 713 md 763 K,
as long as 2111). l5%ilr? t ~wdnm waq i n ~ ~ ~ k s c d sharply
and c.f~nt,inuoiisly w h ~ n aged at 813 K, mc1 wachrd its
p ~ a k Y ~ I U C , i.e. 540 HV, after aged for 4 h, a t 1 then
dccr~amd sIi~htly with Increaqing aging time, corre
s~iflnding to a relatively good ivsistarrce agd1~4t OW-
aging. For ovw- ~ml rondifioa, r.c. R73 K, tlw hacd-
ncss increaqd quickly at i.hc beginning, But began
tadrop a f m aging for mow thrm 1 11. Thr cflrcts
of t11e various heat. treatments, wgecidly t h ~ aging
trentrnpnts, on a, by, dongation (d), d u c t i ~ n in
area id), and irnj~act toughnrs arc! ah- in TdJe J
and Fig.3. 'Lbhc ST md CT samples m e quite low
in gtr~ilgth. nnd high in toughness. Drlrinig the w-
ing trmtmeot, t h ~ my and q, nf t . h ~ steel incwwd
mntineacrs1.y with increkqing the aging tmpcratrue
wd rparhrd their maui ~mm valacs on l*ng at 813 K.
Above XI3 K, the strength droppd signiticantly, i.e.
ovrl--&ng; arid thc unpact toz~ghnesq ;slmmascd con-
tin~iorrq[y. Eqwially, tS and cl ~ ~ncr~asPcI slightly on
aging at 873 Tr' cotrtpad with that nf at 613 K.
Menu
Fig.8 Mw.t d aging temperature (for 4 h) on mmachmkd prophi es d the expwirnentd st el : {a) ulkimate
Itcnqik strength, nh; D,2% p m l yield strength, my and impact toughas, [b] reduction in area, d~ and
dmg~kion, d
Pipl.4 TEM imp xnd mu l t ~ of the mic+ast+u&un?a & z a p d ST and CT specicimms: (a) bright field
[BF) irnry;~ of thc strriet~m after ST and oa6ling to room t mp ~ a t m, with arrows i ndi t i ng wtaincd.
austenite films, and markmite laths with a high dwsity d <lislmtioia, [h) mrrqondinp, SAD pattern
from the 101117 and [fl01]C? zone m, [c} BF i m ; ~ with cmmsponding SAD pattern from r h ~ i l ll]e m n e
=is, showing a fi ~l l y martensitie rni mtrudtur~ af kr CT, [d) XRD pattmn of swi mens
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Table 1 Ifeth~uical propartie at ltstrvl atwl iu different h~rct trmtm~nt conditions
Conditions ub/MPa rrY/MPa 6/% dl% l mpact t ot ~gh: ha~/ J
s.l.l> 1095 :I); 20.0 73.8 2;n
CT*) 1297 773 18. 5 654,R 234
AT=) at
713 K 1675 1426 19.5 57.8 1 fl0
763 K 1790 9 600 17-F~ 57.0 71
813 K 1940 1774 16,3 56,3 50
873 K 3645 3 220 19,O 5g.5 47
Nates: 11 S7-%1111tion twatmmt at 1323 K for I h+air cnaling;
2) C'l'
ST+cryopnical!y trestmmt st 2tIt1 K for R h; 3) AT-SrJ'+CT+nging tmtmmt
f t r 4 l a aL rligcrcnt Lrmprrrtlrrm
3.3 Mi mt n ~ c r ~ l r c ~aturatrrl mrten~it~ir: n~atrix, rn mentioned by , vt l ~e~
rwarcl~~rd"-"~. The formation of such clustm was
Tlie p r d o r n i n a ~ ~ t phwc irr the ST spm:i m~n uraq
t l ~ o u ~ h r , to In xsi st d hy pipe difi~sinn t'timugh h e
lath rnart ~nai t ~ wi l h a high dl rl oca~i on dcn6ir.y. In ,;_, lnr.rr;wmr .I:rlnnnC:n.rr :- +C,n enl,rF trnq+nA
lath martensite rnkmtruct,r~re, a4 shim in Fig.4[~].
XIEiD a~~dp*;rti in Fig-4[d) a1w proved t h w TEM re
s111ts<
Figure 5 shorn TEM imag~s of t h ~ exp~r i mm-
td gkwl altw agjrrg at Y ~ ~ O I I R tprnperatures for 4 h.
When agd at 763 K far 4 h, it is significmt. that a w
marM by t.hc n mwu jn Fig.S[a), clrrly n smdl r.01-
ume fracti on of pl ate-sl rapfl p w c i p i t a l ~ m e fc11111d
in a sira~1~ l at h dmar t mxi t e, but Lhis had a l r ~ d y rr-
soltecl in thr: sharp inmease i t i hmclnes and gtwngth
compared wi t h that of ST or CT conditions as slloivn
in TaI~lp 1 and Fig.3. Similarly. TVF can p r ~ d i c t t11m
xbr aging at. 713 K for 4 h, t.hc F+R"i-Mo atnm or
nthcr type 01 clnstcm nia~sl be formed in the super-
D'CllL 411C pl l l l l r l j Jl C 11t I 1, Ul ~CW C U 'LUDLULQI.IVJI Ul UWUU
under thi s rnechanjsrn~~~~~~]. the 813 K peak-aged
spwci~ncns, homogcnmus, fine precipitatm, primarily
containine manensite laths, RTFE fonnd, as shown
in Vig.5tl.r). T11c size rlisfribution d prmipitatm i s
sho~'11 in Fic.B{c] and thc me,m prccipitat~l oi7e mm-
wr r d WRS a110111 8-in nm* awuming a spl~r~isal par-
r.icle morphnlogy. Thc awragp inwr-partide spacing
war; lcm than 25 nm. At the Piigh~sl aging tempera-
t u r ~ nf 873 K, n slightly i n m~ ~ wr l v n l i i m~ fr,act,irm of
l ha precipitate, f unl r r r ~o:rra~ni ng or t h ~ prwipitatcs
and even rn~rging with thrir nrigl~hom (Mack arrtnvs)
H~PTC RWII and dcmonsi t~~nl ed irr Fig.S(d); rnorcarrer,
nlthwgii austrnitc was noi foiind in TEM image, a
fraction or s~istcnitc xras rletcrmincd by XRll
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Fig.6 SEM Frmture mf i m af impact toughrrm speimenr: dhr CT and AT at 813 K: [a] CT, (b) AT at 813 K
3.4 Fkactography
Figure 6 wbows Erclcture surfam of the impact t&
specinlens &r CT anrl AT at 815 K for 4 h. It is
evid~nt that aher CT, thn kacture siarface consisted
mainly of fine dilnplm as shown in Fig,6(a), which ex-
hibited m entirely transgram tar r u p t ~ ~ ~ c mode known
as microvoid coal csmc~. Also, there wee some: large
dimplm in sOmp regions, in agnxnlent with the high
fracture taughas~s aftfir this treatment. However, the
rupture mad^ of the specimen hcga.n to change from
ductile to a I~rittle appvzuanw when a g d at 813 K.
It cwr bc wen tirat ffnilur~ had ocrtirrcd wia a mi x~d
mode of ductile and clcawgelikc Iracture, shown
in Fig.G(b).
4. Discussion
Aa a PH maraging stainlrss stccl, mow than
Bl%Cr waq added in ardm to wsure its goad mmsion
mistmce. Also, a quantity of Xi nra5 uml to halance
Cr and obtain a wholly martensite matrix mr d i n g
to thc Schafllefs diaRram123]. However, Mf temper-
ature of tt~sted stml is abu~~t 213 K, and the s t e l
has to be cryoppi dl y treated t o obtain a maitensite
structure b~Tow @ng. Espceially, Co was <adr l ~I in
ordm tn ml~mice thr hd formability of the steel and
l o w the solubility of Mo in the martensite matrix,
so that there would be more Mo taking part in the a#-
ing react-ion to stmgthm tlre steel. Thi s inberution
was called the synergistic effect of Co and h ~ [ ~ * ~ 7 ~ ~ 1 .
Fufihwrnolc, prwipitaka wntaining Mo iwe likely to
form at higher ternpcratum and longer sging t i me
than Ithose containing Ti w C U [ ~ ~ ' ~ ~ ' ~ ~ , which W.W &O
p r d by the optirnum aging pararnetws, i.e. 813 K
for 4 h. Theti, preripitah msrltaining Ma, e.g. FezMo
and F e 7 M~ , arc likcIy to form in thc dlql2'34, and
R phase i s drw, the msible pmipitaw based on other
rarar&ersf resultlP"2~1 h9 ~ 1 1 . But the SAD patr
kern corresponding to p d - a & TEM image WBS not
enough, which was not illustrntcd in the pr mnt
paper, So the exact precipitnatc t y p ~ nwd tc, LM! con-
firmed in ht ure study.
For PI1 sml , the stren thening mechanism can
be assumed ai Eq2(I)*.m73fl, where 0,. as, on, o,,
and udqc are the uy contribution from the match,
d i d ml~it.ion strcngthcni~~g, grain boundary h a d -
ening, prrrcipitatimr hardening and [dislocation m d
substructure] harbming, respectively. Tbc sum of
[ ~ ~ + u ~ , - t - t ~ ~ - t r ~ ~ ] i s equal to the d u e OF ay in the
CT condition, it. 773 MPa, which neglects tbcir in-
ter& on strength. In our prcviou~ study, the influ-
of ST on prior austeniM grain [PAG) size and
mechanical property hxs been it~vcstigated, %.c. PA6
si z~, and nr obey the Hall-Petch h
addition, it was found that pr~cipitation hardening
plays the most. impcsrtmt role in strengthming of this
steel. As a mult., several i n ~ e s t i ~ ; r t o r s [ " ~ ~ ~ ~ ~ ~ ] haw?
proposed that stmgthening can bc amounted for by
an Orowan tncchxni~rn1~~*"-~~{ S.e. Eq.(2],
whew u, i.4 the total yidd strength, ut~ thc matrix
yield strength, T the line tension, b thc Bur ers r w-
tor, and b the interparticle spacing Det ~rt [~~~uzt i Ii md
the cxpre~lsion put hrth by Ansell and ~ ~ ~ n e l l ~ ~ * . " ~ ! to
argue that a ~igflific~fkt contribution b t h ~ strength
corncs from the hidl shew strength of' the precipi-
tates. Hmwr, it seems that if t h ~ matrix strength
was tdwn into acwunt, a yield s t r ~ngt h considerably
higher than the o b w d me, which would have hen
predicted. Thc following is xn attempt tu predict thc
strengthening mehanism. The uy of the 18Ni[250)
steel predicted by 3 modified mod~l of the Orowan
rplationghip, i.e. F4.[3), was in god agreement with
t he experimental d u e of 1640 ~ ~ a l ~ ~ 1 . The dt he
peak-aged ($13 K, 4 h) and over-aged (873 K, 4 h)
conditions were cstirnatd in the prewnt study, us-
ing the mean particle sizes and interparticle spacings,
which were remlily measurable. The s phwi d p mi p
itates in the pcak-aged and arm-aged conditions were
approximately 10 nm and 30 nrn in diameter Id), r e
spectivcly. Taking the vnlumc fraction of precipitates,
j, a? 5% fnr the pak-aged c~ndition,Rf~~] and 7.5% for
the wer-BglLd condition, interparticle ~pacings, A, of
16.7 nm and 58.3 nm were obtaind by using the a-
pression ~ ' ~ ~ = [ ) . 8 2 6 / ~ [ ~ ~ * ~ ~ ] . Then uy was estimakdl
by the following equation:
where G is the stlcar modul ~~s d the matrix, 4
is related ta the Poisson's ratio of the matrix by
$=I1 + 1/(1 - v)]/2, v is the Pi~.c:on's ratio of
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t11~ ~mttiY, taken as 0.3["1~~1: the o t h ~ r tcmis, haw
the same ~ne~lning~ as abm. Thing G=71 GPa,
k0. 249 nm1291, and fl0=T7S MPa, tllc calculatrd fly of
1G0 and 1260 ?dPx here ~btaincd for the p d - q e d
and m-agerl conditi~ns, in g md agrmmwt nit11 r he
ex?xperirnen~d data.
Tn w m m q , the whde strengthening pmrm nf
the prsent stect can b~ consi d~rd to b~ as follows.
(1) After CT, the st-1 matrix consisted of martrnrtite
with R high dpngity of di~locations, which myurerl the
basic hall strength of tllp steel. Ttw incwrnei~t of
s t r ~ngl h r m r t h ~ ST rmditiorr was dale to f hp dirni-
nation of r e h i n d austmrite. (2) Then, in thp initial
&'I~PS of aging, the sf.rmgt.hming wm attriht.ab\c t r ~
t . hr- ~t res ;srr~dd for disiocrcations b crlt fhrnugh the
mhm~tt: elertaents c1ust~rs and/or the prwipilates.
lI.rawcvm, thr strcngtli did ml reach i ts peak value
at t 11i ~ stage, bccau~, even thalgh t hee r l u~l ~r r t ~ and
pmipitatrs were rff~ctiw for pinning thp dislocations,
t-llcir wlnrnc f r mi on was too anal1 and t hi r i nt ~r -
pasticle spacing wm hug^$^^. (3) 11s thc prt!r:ipitatw
cm~sen w ~ d thpir wlumr fraction inrrcasm, ~ h c stress
n m f d for dislocations to cut thmugh them i ncmaqd
which 1 4 to an incr~asc in 0,. Finally, thc prwipi-
tat* v w tn a eriticd s i ~ d ' ~ ] and their r~lurne frac-
tion alsn reached an optimum dr r c, mrmponding
zhc dongatinn md rduction d area w ~ r e 16% and
,56?4% mpect-ively* and the Charpy U notch toughl~cr~s
was awr 50 J. This mmbination of prnpM8icrr ~xcml s
the highwt Iewla prcvio~~sly r~ported for a ~naraging
staipjl1lPSs stwl.
(2) Aftaim aging at 873 K for 4 11, the prccipitnt,k%
in the cxpctimmltal s t ml rrhnw a high volume Frmim
and critical sizr, and a. ~~rliform dispersion.
(3) After the snlntian treatment, relain~d allsten-
itc filnis r~nmined along the rr~artcnsitc lath bound-
aries in the matrix I.11~ stwl duc tcr t h ~ r d ~ i v d y low
:14r tmperaiure. Thp ~ c t a i n ~ ~ i a11stmib ws taran$
formed to mr ms i l c by a crppni c trcatmmt at
200 K that wxs bl ow the ,'idr ternpcraturc and an-
tributfcl to the stwl atmilling high stm~gth.
Arknowf~dprnentrr
This wurk was p ~ l y fitrppmd by khc h d of Na-
tional Hjg11-Tda De\ ~Bapm~nt Projmt or China ["8&3"
Pr%~rsm, Yo. ?UR?AASOfrIO5]1. Aslrl thc author, K.Liri,
dm, expr- ~ecknmr l cd~ant tr, Dr. Wi1li;am lN;lrkr!
fmm Rp Aarocn for mpnding the paper and t o &. Yi
We fmzn hharatory of Mat~riais Scic~~cc, b l f t Uaivvrsity
of Twhncrlou, €or cnlightraing &wus~ir>ns.
whirh Id to A c-ritird interparticle spacing arid t l ~c
djsloc;ltiona werr forcd lo bow wl bfinqrn +,hPm in-
[I ] W.J.Chen, Y.Y.itru md S.X.Shen: 3. Mater. Sci,
s t ~ d of t~rtt~ing through thmni"]. (4) Aging at higher
'Ikhnol., MW, 20[2], 217.
mp e r a t u r ~ , for example 875 K f i i 4 11, hcsider re
12 1 r,.D.\I'ang, I..ZH.Jiang. 31.i.n~u, X.Lir and W.M.Zhou:
.F. Afatrr. Sci. Twf!noJ,, 2005, 21(5), 710.
t ~ t l ~ a u ~ t c n i ~ m d ~ ~ e t ~ a n d ~ m ~ ' ~ i ' n ~ d b ~ [ ~ I D . R . ~ ~ M ~ ~ ~ , ~ , ~ , ~ ~ ~ ~ ~ ~ : ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ s ~ -
~ t h ms ~ ~ - ~ ~ l " l , the further i i nmc8~ in partirl~ si7e and o n r ~ and Engmwrinrf 'I'singh~ia Lniwrsity Prm, %-
spacing dm rcmlultrd in t i rlecwaw in s l ~n@l i , in ac- jing, 2005.
cordante with thc Omwan ~nechani..m. [4 ] Y.IIe, X.Yang, W.S.Qn, I'.Y,Kolrg and G.Y.Su:
Inkresting h- t t am of the ttenuile Wts 01 the mu- Matep. Sci. Tdnd. , 2003, 29, 717-
plm a& at 873 K m e thr dcr r ~mo in the ratio nf [j 1 Yi HE, IIr TATG, bknva KOKG, Wenqhcng QX and
uy t o rrb and a slightly increase in d ant1 dl as well,
Gnoyue SU: Acta MrfaJ!. Sin.. 2002, 30{3), 278. (in
a~ shmn in 'F~blc I and Fig.S(a).
AR prgdit:Wd by Cbinrsc)
Sinha et a6.1331, it appeam that kherc is a change in
[ 6] Y.HP, K.Ymg, W.Sha and D.J.CIelmd: McesrM.
M~ltrr. Tram. A, 2W1 36, 1.
t tie hilhavim of this type of ~t r cl ah: the yield point
l7 1 H,,, K.l-mg, l Y. S. ~u, F.Y.KonF: G . Y . ~ ~ ~ :
kca~i w of the pmmce OF R mf t ~ r phm, srlrh as
Marfir. LP~L., 2002, Sfl, 763.
auut~lrite. ID other nards, n'hen the strcss excccds
[R ] J-J iycbtpr: nmP. A.SM, IBN, gl+ 816.
, - 3 . , , . . 3 % . . r I . r
or IQhgm aging Irlmeb. 30, it can b e dM11wrl r.t~sst the
dchritcittiort i ndi ~ml transformatian of ausltmiltc to
martmsitc abow the yield p i n t cm~l d hc responsible
for thit highcr tPnsile slrcngth, which would 1~md to a
lower raiio day myr ub.
{I] Thc optimum heat t.rentmpnl For mxxirniirn
st ~mgt h in the new ultrahigh strength rnnragi~ig
stainlrss steel was rletermira~d to h~ aging for 4 11
at 813 K, following mlutiorl and cryogenir t r ~ a t ~
mmts. 1Fritlli this tmatm~nn., the 6, and b,, of t h
s t e l remhd 1773. StPn and 1940 MPa, r~prct i wl p;
- 7 - - - -
[13] G,?V,TuCTncll and RL,Cairns: Tkms. ASM, 1968, 8E,
7%.
[I41 Y.Kambr, K.Knh7awa md S.Muaeki: ?Mswtn-
Nnpne (J. Iron SIW! Inst. Jpn], 1976, 62, 1229.
[I51 H. J . ht , k: Aafarrr. Sci. Eng., 1978, 34, 2M.
[IG] Ifr.Sha, A.C~mzo snil G.D.W.Smith: d1I~t . d. B~RA.
A, 1993, 24, 1221.
117 M. Al ~~nml . H.Ayub, I.Na5in1, F.H.Hashmi and
A.Q.Iihan: Maker. Sri. Thnd., 7995, f 1, Y2Rl.
! I S] K.3 ill=, F.Dmrrix and M.liithmtrand: ~Mat ~r. 9;.
r n ~ . , 1998, A2511, 22.
[I91 C.N.Hsiao, U.S.L'hinrl snd d.RYmg: Ma&. CI?rm.
Ph-p., 2 M2 , 74, 1.74.
[2D] M-Watt~nstrand, J.O.Kilma, K.S#llw, P.Liu and
?d,~lndm?on: Acre 5IctaJJ., 2004, 62, 1023.
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318 J. Mvlater, Sci. Techno!., Vo1.23 Nn.3, 2007
1211 U.K.Vimmathan, G.K.Dey an8 M.K.As~\ndi: Metdl. [30] A.S'h~khta, H,I.karofison, M.K.Miller, S.Ib.Rinwr
lhmg. A, 1993, 24, 2429. and E.V.Pcreloma: Metall. ;Water. Ttans. A, 20~14,
[22] P-Lir, A.H.Stigenbmg and J.O.Kilmn: Acta Metafl. 33, 973.
Maker., 1994, 43, 28R1. [31] K.Liu, Y.Y.SLan, X,Y.Yang, J.X.Liang, L.Lu and
[23] Ij.K,MndaL and R.R,aj: Hig& Nitmgen 5-Lr: and K.Yang: J. Mater. SL~. TecJ~ad, 2006, 22(G), 769.
SLainlw SteeLqz Nxosa Publishing Horw, NPW Dell~i, [321 M.Mart~yama, K. Hm, M. Sw and M.Kiky&i:
20U4. 1Mat~1. %J. Eng A, 1998, 230, 127.
[24] W.Sha, A.Cmwa and G.D.W.Smith: McMJ. Trans. [33] P.P.Sinha, K.T.T'hzvian, K.Srcekumar, K.V.Nagamjan
A, 1993, 24, 1233. md D. S. Sma: Mater. Sti. M~ n o l . , 1998, 14, 1.
[251 W.Sha, A.Cerezo and G.D.W.Smith: Met&. Tkans. [MI V, K. Vasud~van, S.J.Kim and C.M.?Vayman: - 4f et d-
A, 1993, 24, 1241. naos. A, 1990, 21, 2655.
[MI H. RH. Baj~isimi: Mater. Sci. Eng. A, 2002, 333, [%I K.Debrt: Trans. 9. AS-If, 1968, 53, 262.
147. [Xj G.S.Anw11 mil F.Xr h r l : Ad a Metar! a Z!360a R, 612.
[27] J. O, Wi l m, A.R.Stigenberg and P.T,iu: Me M. [37] G.S.Ans~ll: Act a Metall., 1961, 9, 518.
134ater. Tkm-A, 1994, 26, 2225. [3~] Z.Guo and W.Sha: M~tall, Tkans., 20012, 43, 1275.
p3] K.P.aalan, A.Vmugapal Rddy and D.S.Sarma. [39j I3.L.C- mrl A . R ? V i w J. Imn S t d J d . , 1963,
Sr. pt a kfetdl., 1999, Sg, 902. 21)8, 600.
1291 E.V.Pmlama, A. Shekb~~r, M.K.Miller and 1401 V. F. Zxhyl E.RParLr, D. Wm and R.Bnsh: Tkans,
S.P.Ringcr: Aet a M~tdf., 2004, 52, 55R9. ASM, 1%7, 80, 252.
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Effect of Aging Condition of Tensile Properties
of Iron-Nickel-Titanium Maraging Steels*
By Kii SOENO** and Masatoshi TSUCHIYA**
Synopsis ty.9,17)
Resirtivi@ change during isothermal aging and the associated tensile
Fe-Ni-Ti ternary maraging steels have not yet
properties have been investigated on Fe-IONi-1.8Ti, Fe-I5Ni-1.8Ti
been throughly investigated on the effect of aging
and Fe-20Ni-1.8Ti maraging steels. I n order to investigate the effect of
condition on the strain rate sensitivity in ductility.
strain rate on ductility, a crosshead speed was varied from 0.005 to I 0
~ h , present paper is concerned with the tensile prop-
mmlmin.
erties and their strain rate sensitivity of the ternary
Embrittlement caused by the decrease i n strain rate i s found i n' t he
maraging steels containing Jine and coherent precipitates, formed i n the
maraging steels.
j rst precipitation process. Brittleness independent of strain rate i s also
found i n the Fe-IONi-1.8Ti and Fe-I5Ni-1.8Ti maraging steels
strengthened.fully by the Jirst process at lower temperatures. Both cases
result from the slip character that intense slip bands tend to be formed
during deforming. Tensile properties which are ductile and insensitive to
strain rate are obtained after subjecting to the second process. Aging
structures i n which intense slip bands are dzficult to be formed during
deforming are concluded to be suitable for the improvement of ductility.
I. Introduction
I t has been known that Fe-Ni-Ti ternary marag-
ing steels are possible to be precipitation-hardened.
Fe-ZO%Ni-l.G%Ti and Fe-25%Ni-1.6%Ti steels
have been developed for practical use. Many inves-
tigations have also been carried out on the precipitates
in the ternary maraging stee1s.l)
The ternary maraging steels containing relatively
high titanium contents have been considered to be
less ductile than 18 % Ni type maraging steels con-
taining cobalt, molybdenum and small amounts of
titanium. This fact was considered to be attributable
to the preferential growth of precipitates at prior
austenitic grain boundaries or lath b o ~n d a r i e s . ~~~)
Mishima et aL4) reported that the ductilities of Fe-
8XNi-Ti ternary maraging steels were closely related
to precipitated phase: The decrease in ductility was
much more evident in the precipitation of CsC1-type
NiTi than in that of DO,,-type Ni,Ti.
Soeno et aL5-s) have reported investigations carried
out on the strain rate sensitivity in ductility by using
nickel maraging steels containing cobalt, molybdenum
and titanium. Embrittlement caused by decreasing
strain rate has been observed in the maraging steels
containing coherent precipitates which are possible to
be cut by the movement of dislocations. Ductility in-
sensitive to strain rate is possible to be obtained, when
the precipitates contained are relatively difficult to be
cut by the movement of dislocations and intense slip
bands decrease to occur. Stress concentration built
up at grain boundaries during the course of plastic
deformation is possible to be decreased by the refine-
ment of austenitic grains. Accordingly, the refine-
ment is also needed for the improvement of ductili-
II. Experimental Procedure
Raw materials for alloy preparation were electro-
lytic iron deoxidized by adding 0.1 % A1 in vacuum-
melting, electrolytic nickel, electrolytic manganese,
and titanium melted in a consumable electrode arc
furnace. For the elimination of carbon and nitrogen
contained in the vaccum-melted iron, the iron cold
rolled to 1 mm in thickness was subjected to annealing
for 24 hr at 650 "C in wet hydrogen, and cooled at
pressures around low5 torr. The purities of the alloy-
ing elements were more than about 99.9 %.
Ternary maraging steels with the nominal com-
positions listed in Table 1 were prepared by arc-melt-
ing in an argon atmosphere, using a nonconsumable
tungsten electrode and water cooled copper crucible.
The ingots were turned and remelted triply to achieve
homogeneity. As the weight loss during melting was
very little,2J0) the nominal compositions were accepted
for the alloys. All the ingots were homogenized for
8 hr at 1 050 "C in a vacuum of torr, hot-forged
and homogenized finally for 1 hr at 1 100 O C in a
vacuum of torr. Plates cold rolled to 1 mm in
thickness and wires cold drawn to 1.5 mm in diameter
were prepared for tensile tests and for resistivity mea-
surements, respectively.
All the alloys were solution-treated for 1 hr at 900
"C, and quenched in water. Prior austenite grain size
numbers were in the range 6.5 to 7.5. Aging for 300
min and less was performed in a salt bath. In case
of aging more than 300 min, specimens aged for 300
min in the salt bath were quenched in water, washed
and then reaged at the same temperature in a high
purity argon atmosphere sealed in a furnace. The
Table 1. Chemical compositions of Fe-Ni-Ti ternary
maraging steels used. (wt%)
-
- -- - - -
- - -- -
Ni Ti Mn A1
10 1 .a 0.1 less than 0. 1
15 1 . 8 0. 1 less than 0.1
20 1 . 8 0.1 less than 0.1
-- - - - - - - - - - -
- - --- - - -- - ------ - ---- - - - - - - - - - - - - - - - - --
*
Originally published in Tetsu-to-Hagant!, 68 (1982), 309, in Japanese. English version received September 3, 1981. a 1982 ISIJ
** Hitachi Research Laboratory, Hitachi Ltd., Saiwai-cho, Hitachi 317.
[ 848 ) Research Article
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Transactions ISIJ, Vol. 22, 1982
1849 ]
form of the specimens used for tensile tests is shown in
Fig. 1. After aging, the thickness of the specimens
was ground off from 1 to 0.3 mm by using a centerless
grinder. Crosshead speeds used in the present inves-
tigation were 0.005 (strain rate, i = 0 . 7 6 ~ sec-l),
1.0 ( i k 1 . 5 2 ~ sec-I), I0 mm/min (i = 1.52 x l owZ
sec-l). In order to investigate the precipitation be-
havior in the alloys, resistivity change with aging time
was also measured at liquid nitrogen temperature by
the four-probe potentiometric technique.
III. Results
I. Fe-IONi-I. 8Ti Maraging Steel
Figure 2 shows resistivity changes, and tensile prop-
erties are given in Figs. 3 and 4. Each point of
tensile strength or total elongation in the figures rep-
resents the average of three to five tensile test results.
A uniform elongation can be measured from a load-
elongation curve with a local elongation. No sys-
tematic influence of strain rate on uniform elongation
was found in the maraging steel investigated by using
the cross head speeds.* Each point of uniform elon-
gation in the figures represents the average of values
measured at the cross head speeds. When fracture
with local elongation was not observed at the cross
head speeds used, uniform elongation was not shown.
The existence of two precipitation processes has
already been shown in our resistometric investigation
Thickness: 0.3mm
of the precipitation in Fe-Ni-Ti maraging steels simi-
lar to those used in the present investigation.10) Ar-
rows in Fig. 2 express that the resistivity decrease due
to the second precipitation process becomes evident.
The precipitate phase in the first process and that in
the second process are, for a while, referred to PI-
phase and P,-phase, respectively. From the com-
parison between Fig. 2 and Fig. 3, the strain rate
sensitivity in total elongation is found to be evident
in case of being not fully strengthened by the first
precipitation process. Total elongation decreases with
the progress of the first process, and increases with
the decrease in strength due to the progress of the
Aging time(min)
Fig. 3. Tensile properties of the Fe-1ONi-1.8Ti maraging
steel aged at 500 "C (a) and 525 OC (b).
Fig. 1. Tensile test specimen.
I I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
500'~- Aging
I I
8 -12 -
h
. A
.-
2 -14 -
'--•
.-
Ln
L1: -16 '
I 1 1 , 1 1 1 1 1 I I
10 I o2 1 o3 1 o4
Aging time ( min
p,: Specific resistivity after solution-treatment
pt :
Specific resistivity after aging
Arrows express that the resistivity decrease due to
the second precipitation process becomes evident.
Fig. 2.
Resistivity change at liquid nitrogen temperature
Aging time (mi n )
during isothermal aging of the Fe-1ONi-1.8Ti mar- Fig. 4. Tensile properties of the Fe-1ONi-1.8Ti maraging
aging steel. steel aged at 550 "C (a) and 575 "C (b).
-. - .- - - - - - -. - - - - - - - - - - - - - - - - - . . - - - . -- .- - . . . - -
* This fact was also found in the Fe-15Ni-1.8Ti and Fe-20Ni-1.8Ti maraging steels.
Research Article
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( 8 5 0 ) Transactions ISIJ, Vol. 22, 1982
second process. For the maraging steel containing
the P,-phase precipitates, the decrease in total elonga-
tion is not found even in tensile tests at a cross head
speed of 0.005 mm/min.
Figure 4(a) shows that the decrease in total elonga-
tion with the progress of the first process is evident,
as seen in the specimens aged for times in the range 10
to 100 min. The strain rate sensitivity in total elon-
gation is also found in the specimens aged for rela-
tively short times. Uniform elongation increases with
aging time in the range of the second process. An
increase in total elongation by the progress of the
second process can be attributed mainly to the in-
crease in uniform elongation. This fact is also seen
in Fig. 3. When an aging temperature is raised to
575 "C, total elongation becomes insensitive to strain
rate after relatively short times of aging (see Fig.
4(b)).
Figure 5 shows the relation between tensile strength
and resistivity decrease, constructed by comparing
Figs. 3 and 4 with Fig. 2. Aging up to the time when
the resistivity decrease measured during aging at 500
"C, or 550 "C reaches -8 to -9 pQ-cm is regarded
as the first process, as seen in Fig. 2. Figure 5 shows
that tensile strength at a given resistivity decrease in
the range of the first process is evidently less for aging
at 550 "C than for aging at 500 or 525 "C. I t is con-
sidered that the P,-phase precipitates are mixed during
the course of the first process at 550 "C and result in
the decrease in strengthening. The decrease in total
elongation with the progress of the first process is also
1 0 5 0 0 " ~ - ~ g i k g
I " "
Fig. 5. Tensile strength us. resistivity decrease of the Fe-
10Ni-1.8Ti maraging steel.
I I I I , , , , , , I I I I 1 1 1 1 1 1
to lo2 lo3 1 o4
Aging ti me (rni n)
Fig. 6. Resistivity change at liquid nitrogen temperature
during isothermal aging of the Fe-15Ni-1.8Ti mar-
aging steel.
less for aging at 550 "C. In case of aging at 575 "C,
the resistivity curve measured shows that the second
process starts after short times of aging. Thus, ductile
tensile properties are obtainable after short times of
aging at this temperature.
2. Fe-15Ni-I. 8Ti Mayaging Steel
Resistivity curves and tensile properties are shown
in Figs. 6, 7 and 8. The existance of two precipita-
tion processes is also seen in the resistivity curve at
525 "C or less. As seen in Fig. 7, the variation in
elongation with aging time at 475 or 500 "C is similar
to that found in the Fe-1ONi-1.8Ti maraging steel
I I ' ' " " " I ' " " " ' I " I
Aging ti me (mi n)
Fig. 7. Tensile properties of the Fe-l5Ni-1.8Ti maraging
steel aged at 475 OC (a) and 500 OC (b).
-0- 1.0 mmlmin
10
01' ' ' " " " I
I I
10 1 02 1 o3
Aging time (mi n )
Fig. 8. Tensile properties of the Fe-15Ni-1.8Ti maraging
steel aged at 525 OC (a) and 550 "C (b).
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Transactions ISIJ, Vol. 22, 1982
[851 )
aged at 500 or 525 "C; total elongation is sensitive to
strain rate at an early stage of the first precipitation
process and decreases rapidly with the increase in
aging time. When an aging time is lengthened in
the second process, total elongation increases with the
decrease in strength and becomes insensitive to strain
rate.
In case of aging at 525 "C, the strain rate sensitivity
in total elongation is found in the specimens aged for
times in the range of the first process (see Figs. 6 and
8(a)). I t is also noted that total elongation decreases
less rapidly with aging time in the first process. The
P,-phase precipitates are considered to be mixed dur-
ing the course of the first process. Tensile properties
of the specimens aged at 550 "C are ductile and in-
sensitive to strain rate, as seen in Fig. 8(b). The
resistivity curve measured during aging at 550 "C does
not show the existance of the first process.
3. Fe-2ONi-1.8Ti Maraging Steel
Resistivity curves and tensile properties are shown
in Figs. 9, 10 and 11. Soenolo) has shown that the
resistivity of this maraging steel increases during the
very early stage of precipitation and then decreases.
Because of this initial process, resistivities after short
period of aging at 450 or 475 "C are larger than those
immediately after the solution-treatment (Fig. 9). I t
can be also seen in Fig. 9 that two processes appear
in the resistivity curves measured during isothermal
agings at 450 and 475 "C. As the initial process as-
sociated with the increase in resistivity ceases after
very short period of agings at both temperatures,
aging process till the beginning of the latter resistivity
decrease is referred to the first process for convenience.
As seen in Fig. 10, the strain rate sensitivity in total
elongation is found in the specimens aged for times in
the range of the first process. Specimens aged at 500
"C for relatively short times show also the strain rate
sensitivity (Fig. 1 1 (a)), although the first process is
not clearly shown in the resistivity curve at this tem-
perature (Fig. 9). Tensile properties which are duc-
tile and insensitive to strain rate are obtained, when
the P,-phase precipitates are increased by lengthening
aging time or by raising aging temperature. The
fact that the rapid decrease in total elongation with
the progress of the first process is not found in the
maraging steel will be discussed in the following chap-
ter.
I V. Discussion
Extensive investigationsl1) carried out on the de-
formation of precipitates and on slip line observation
in deformed alloys have shown that dislocations are
possible to pass through small coherent precipitates
and intense slip bands tend to be produced in alloys
containing coherent precipitates. I t has also been
known that cross-slipping is relatively difficult to oc-
cur in maraging steels containing coherent precipi-
tates.12-16)
I t is natural to conclude that the PI-phase is co-
herent with the matrix. Therefore, it is considered
that intense and straight slip bands tend to be pro-
-8 L1
I I
10 1 02 1 o3 lo4
Aging ti me ( mi n
Fig. 9. Resistivity change at liquid nitrogea temperature
during isothermal aging of the Fe-2ONi-1.8Ti mar-
aging steel.
Aging ti me ( mi n)
Fig. 10. Tensile properties of the Fe-20Ni-1.8Ti maraging
steel aged at 450 O C (a) and 475 OC (b).
[ -0- 0.005 mml rnin 1
- 4 7
Aging ti me ( mi n
Fig. 11. Tensile properties of the Fe-20Ni-1.8Ti maraging
steel aged at 500 "C (a) and 525 OC (b).
duced across grains during deforming the maraging
steels containing the PI-phase precipitates. Intense
stress concentration may be produced in regions where
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[ 852 ]
Transactions ISIJ, Vol. 22, 1982
intense and straight slip bands are blocked by grain
boundaries or intersected by other intense slip bands.
Steps produced at the surfaces of a tensile test speci-
men by intense slip bands may also provide the sources
for intense stress concentration.
The strain rate sensitivity found in the ductilities
of the maraging steels containing PI-phase precipi-
tates can be interpreted in terms of the hydrogen em-
brittlement usually observed in steel^.^-^) The de-
crease in ductility with the decrease in strain rate
results from the diffusion of hydrogen, contained and/
or absorbed at the steps from the atmosphere, to the
regions with intense stress concentrations. For the
Fe-1 ONi-1.8Ti and Fe-15Ni-1.8Ti maraging steels,
the brittleness independent of strain rate is also ob-
served after full strengthening by the first process.
The brittleness seems to be attributed mainly to the
very intense and straight slip bands blocked strongly
by obstacles. We regard the grain boundary as a
main obstacle, as the ductilities of maraging steels
containing nickel, cobalt, molybdenum and titanium
have been known to be considerably increased by the
refinement of g r a i n ~ . ~ J ~ ) Under such circumstances,
the stress concentration exceeding the theoretical
strength of the solid may form a crack within the grain
containing the blocked slip band, in the grain bound-
ary, or in the adjoining grain.ls) When an aging
temperature is raised to 550 "C for the Fe-1ONi-1.8Ti
maraging steel, or to 525 "C for the Fe-15Ni-1.8Ti
one, the P,-phase precipitates partially formed during
the first process lead to lowering the level of the very
strong blocking of slip bands, and crack formation in
regions with stress concentrations is enhanced after
diffusing of hydrogen.
The decrease in ductility with the progress of the
first process is less in the Fe-20Ni-1.8Ti maraging
steel. Brittleness independent of strain rate is not
found even in the first process at 450 "C. As de-
scribed for the Fe-1ONi-1.8Ti and Fe-15Ni-1.8Ti
maraging steels, slip bands become less intense when
the partial formation of the P,-phase takes place dur-
ing the first process. I t may be expected that the
P,-phase precipitates formed partially during the first
process is enhanced in the Fe-20Ni-1.8Ti maraging
steel.
From investigations carried out on the precipitates
in the Fe-Ni-Ti ternary maraging steels,lJO) the
PI-phase in the Fe-15Ni-1.8Ti and Fe-20Ni-1.8Ti
maraging steels is believed to be DO3-type Ni3Ti.
However, CsC1-type NiTi has also been considered to
be the PI-phase for the Fe-1ONi-1.8Ti maraging
steel.4j10) DO,,-type Ni3Ti is believed to be the P,-
phase in the ternary maraging steels from previous
investigation^.^^^^^^)
When the maraging steels contain the DO2,-type
Ni3Ti precipitates, less intense slip bands are formed
during deformation. The increase in uniform elon-
gation with the progress of the second process can be
attributed to the increase in strain hardening exponent
n in the form
where, otr, etr: true stress and true strain, respec-
tively
K: constant.
We can obtain n=c, at the beginning of necking.
The increase in n is attributed to the fact that disloca-
tions moving through the matrix leave many loops
around the DO2,-type Ni3Ti precipitates, and, in
addition, the operation of a large number of slip sys-
tems leads to many dislocation intersections. I t is
reasonable to consider that the DO2,-type Ni3Ti pre-
cipitates are difficult to be cut by the movement of
dislocations.
V. Summary
(1)
The existence of two precipitation processes
is seen in the curves of resistivity decreases measured
during isothermal agings of the Fe-1ONi-1.8Ti and
Fe-15Ni-1.8Ti maraging steels. The resistivity of the
Fe-2ONi-1.8Ti maraging steel initially increases and
then decreases with aging time. Two precipitation
processes also appear during the course of resistivity
decrease. The upper temperature limit of the first
process for resistivity decrease lowers with the increase
in nickel content.
( 2)
The embrittlement caused by decreasing strain
rate, i.e., the hydrogen embrittlement is found in the
maraging steels aged for times in the range of the first
process. The brittleness independent of strain rate is
also found in the Fe-1ONi-1.8Ti and Fe-15Ni-1.8Ti
maraging steels strengthened fully by the first process
at lower temperatures. Both cases result from the
distribution of slip bands, or slip character that in-
tense slip bands tend to be formed during deforming.
I t is considered that the precipitates formed in the
first process are coherent with the matrix and are
possible to be cut by the movement of dislocations.
(3) During the second process, the DO2,-type
Ni3Ti precipitates are formed with the decrease in the
precipitates formed in the first process. As the DOz4-
type Ni3Ti precipitates are difficult to be cut by the
movement of dislocations, the formation of intense
slip bands decreases. Thus, tensile properties which
are ductile and insensitive to strain rate are obtained
after subjecting to the second process. I t is reason-
able to conclude that the aging structures in which
intense slip bands are difficult to be formed during
deforming are suitable for the improvement of duc-
tility.
Acknowledgements
The authors wish to express their sincere thanks to
Mr. K. Taguchi for his help in the experimental
work.
REFERENCES
1) T. Suzuki: Trans. ISIJ, 14 (1974), 67.
2) K. Soeno and T. Kuroda: Tetsu-to-Hagani, 58 (1972),
1663.
3)
H. Hosomi, Y. Ashida, H. Namito and K. Ishihara: Tetsu-
to-Hagane', 61 (1975), 1012.
4) Y. Mishima, T. Suzuki and M. Tanaka: Tetsu-to-Hagani,
63 (1977), 496.
Research Article
Menu
Menu
Transactions ISIJ, Vol. 22, 1982
( 853 )
K. Soeno, T. Kuroda and K. Taguchi: Trans. ZSZJ, 19
(1979), 484.
K. Soeno, K. Taguchi and M. Tsuchiya: Tetsu-to-Hagant!,
65 (1979), 665.
K. Soeno: Trans. ZSZJ, 21 (1981), 469.
K. Soeno and K. Taguchi: Trans. ZSZJ, 21 (1981), 618.
T. Kuroda and K. Soeno: Tetsu-to-Hagant!, 66 (1980),
1361.
K. Soeno: J. Japan Znst. Metals, 39 (1975), 1059.
A. Kelly and R. B. Nicholson: Precipitation Hardening,
Progress in Material Sci., X, Pergamon Press Ltd., New
York, (1963).
T. Yasunaka and T. Araki: J. Japan Znst. Metals, 36 (1972),
1202.
13)
T. Yasunaka and T. Araki: J. Japan Znst. Metals, 38 (1974),
877.
14) Y. Kawabe, M. Kanao and M. Muneki: Tetsu-to-Hagant!,
59 (1973), 1388.
15)
Y. Kawabe, M. Kanao, K. Nakazawa and M. Muneki:
Tetsu-to-Hagant!, 60 (1974), 269.
16)
Y. Kawabe, K. Nakazawa, M. Kanao and M. Muneki:
Tetsu-to-Hagant!, 60 (1974), 1613.
17) K. Soeno, T. Kuroda, M. Tsuchiya and K. Taguchi:
Tetsu-to-HaganL, 62 (1976), 220.
18) N. S. Stolofi Effects of Alloying on Fracture Character-
istics, Fracture, VI, ed. by H. Liebowitz, Academic Press
Inc., New York and London, (1969).
Research Article
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METALURGIJA 46 (2007) 2, 97-99 97
I. Kladarić et al.: THE INFLUENCE OF RETAINED AUSTENITE ON pRECIpITATION HARDENING OF ...
Received - primljeno: 2006-06-02
accepted - Prihvaćeno: 2006-09-02
Original Scientifc Paper - Izvorni znanstveni rad
ISSN 0543-5846
METABK 46 (2) 97-99 (2007)
UDC - UDK 669.15´x´24´25´28–194:669–153–157.8:669.112.227.343=111
i. Kladarić, d. Krumes, i. Vitez
i. Kladarić, d. Krumes, i. Vitez, Faculty of mechanical engineering
university of Osijek, slavonski Brod, Croatia
THE INFLUENCE OF
RETAINED AUSTENITE ON pRECIpITATION HARDENINg OF MARAgINg STEEL
INTRODUCTION
the increased demand for high tensile strength of ma-
terials used in mechanical engineering was the reason for
the vigorous development of ultra strong steels resulting
in production of maraging steel in the sixties of the XX
century [1, 2].
superior properties, such as: high ductility, high yield
stress, good hardenability, good weldability, simple heat
treatment without deformations, have led to a widespread
application of maraging steels, not only in the manufactur-
ing of diverse construction components, but also in the
manufacturing of molds (i.e. for processing of polymers,
for pressure casting, etc.).
maraging steels are delivered in solution annealed and,
for this reason, the low hardness and ductility make them
suitable for work treatment. they steel are strengthened
with a simple annealing procedure (ageing), which almost
doubles their hardness and tensile strength compared to
solution annealed state. their heat treatment yields some
advantages also that is; machining to fnal measure be-
fore aging, no danger of decarburizing (C < 0,05 %) and
oxidation [1, 2].
the investigation of the kinetics of structural trans-
formation of maraging steel during heat treatment has the
purpose to determine the conditions for development of
microstructures with good impact on properties. Current
dilatometric studies of solution annealing have shown
that the maraging of steel does not fulfll the rule of M
s

interdependence on temperature and length of austenitizing
as in the case of carbon and alloyed steels. Procedures of
solution annealing of maraging steel are not totally revers-
ible, i.e. they do not result in the same structural condition
of material, but lead to visible phase changes that is the
increase of the content of retained austenite [3].
the main intention of this paper was to investigate the
infuence of retained austenite on precipitation hardening
of maraging the steel X2NiComo18-9-5.
EXpERIMENTAL WORK
the experiments were carried out on four samples φ
6 × 18 mm. the samples were multiple solution annealed
and aged in Netzsch electronic dilatometer 402 eP (table
1.). the use of dilatometer enabled to observe dilatometric
The investigation of the infuence of multiple solution-annealing on kinetics of structural transformation of ma-
raging steels has shown that procedures of solution annealing are not totally reversible. Recurrent solution
annealing results in the increase of the retained austenite share in maraging steel structure. In this paper the
infuence of retained austenite on precipitation hardening of maraging steels X2NiCoMo18-9-5 was determined.
The laboratory experimental tests have shown that the growth of retained austenite share in the maraging steel
structure decreases the hardness after aging.
Key words: maraging steel, solution annealing, aging, retained austenite
Utjecaj zaostalog austenita na precipitacijsko čvršćavanje maraging čelika. Istražujući utjecaj višestrukog
rastvornog žarenja na kinetiku strukturnih pretvorbi maraging čelika uočeno je da postupci rastvornog žarenja
nisu u potpunosti reverzibilni. Ponavljanje postupka rastvornog žarenja uzrokuje povećanje udjela zaostalog
austenita u strukturi maraging čelika. U radu je istraživan utjecaj zaostalog austenita na precipitacijsko očvrsnuće
maraging čelika X2NiCoMo18-9-5. Laboratorijska eksperimentalna ispitivanja su pokazala da prirast udjela
zaostalog austenita u strukturi maraging čelika rezultira padom tvrdoće nakon starenja.
Ključne riječi: maraging čelik, rastvorno žarenje, starenje, zaostali austenit
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METALURGIJA 46 (2007) 2, 97-99 98
I. Kladarić et al.: THE INFLUENCE OF RETAINED AUSTENITE ON pRECIpITATION HARDENING OF ...
changes by controlled an-
nealing parameters (tem-
perature and time).
experiments were
planned and performed
in two directions:
i. solution annealing
with determination of
the temperatures of
martensite-austenite
transformation (A
s
), of
austenite-martensite
transformation (M
s
)
and values of total di-
latation ∆l

from di-
latogram, and calculation of the average coeffcients of
dilatation (α) for the range of heating (ϑ
1
= 20 °C … ϑ
2
=
525 °C) and quenching (ϑ
3
= 700 °C … ϑ
4
= 300 °C).
the content of retained austenite based on average dilata-
tion coeffcients was also calculated. after heat treatment
the samples were tested for Vickers hardness HV1.
ii. Heat treatment experiment of aging after multiple solu-
tion annealing.
after ageing the Vickers hardness HV1 was measured.
Multiple solution annealing
in Figure 1. the aggregate of dilatograms of multiple
solution annealing with the points of structural transforma-
tions (A
s
and M
s
), measured values of contractions (∆l

)
for each sample and the calculated average coeffcients of
dilatation during heating (between ϑ
1
= 20 °C and ϑ
2
= 525
°C) and contraction during quenching (between ϑ
3
= 300
°C and ϑ
4
= 700 °C) are shown.
the growth of the average dilatation coeffcient (during
heating) with every repeated solution annealing indicates
the increment of the content of retained austenite. Based
on the calculated dilatation coeffcients at heating and
quenching a mathematical relation for the determination
of increment of retained austenite content after every
repeated solution annealings was estab-
lished [3, 4].
6
6
% 100
10, 30 10
100 / %,
8, 66 10
Z M
A M
Z
A
α α
α α
α



= ⋅

− ⋅
= ⋅

(1)
where:
%A - content of residual austenite / %,
M
α

- average dilatation coefficient of
martensite (sample A) / K
–1
(10,30
× 10
–6
K
–1
),
A
α

- average dilatation coefficient of
austenite (sample A) / K
–1
(18,96 ×
10
–6
K
–1
),
Z
α

- average dilatation coeffcient during
heating (samples B, C and D) (20 °C
to 525 °C) / K
–1
.
Figure 2. shows the increment of
retained austenite content after every re-
peated solution annealing.
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METALURGIJA 46 (2007) 2, 97-99 99
I. Kladarić et al.: THE INFLUENCE OF RETAINED AUSTENITE ON pRECIpITATION HARDENING OF ...
Before and after the
multiple solution anneal-
ing each sample was test-
ed for the hardness value
Vickers HV1 with load of
9,81 N, and the average
value was determined
from fve measurements
(table 2.).
Aging of multiple
solution annealed
maraging steel
The heat treatment
of aging (ϑ
a
= 500 °C,
t
a
= 240 min) has been
carried out on each sam-
ple after multiple solu-
tion annealings. after
aging of maraging steel
X2NiComo18-9-5 each
sample was tested for
hardness value by Vick-
ers HV1 method (table
3.).
Figure 3. shows cha-
nges in hardness values
after solution annealing and after aging in dependence of
the content of retained austenite.
CONCLUSION
in the investigation of the infuence of retained austen-
ite on precipitation hardening of the maraging steel X2Ni-
Como18-9-5 the following was observed:
- after every repeated solution annealing results the con-
tent of retained austenite was increased;
- the retained austenite has no infuence on hardness in
solution annealed state. the explanation could be a high
hardness of austenite in the high alloyed steel;
- the increase of retained austenite content results in
decrease of hardness value after aging.
Based on knowledge of the mechanism of maraging steel
precipitation hardening (increase of hardness value after
aging is result of precipitation very hard intermetalic com-
pounds from martensite matrix) and considering the above
mentioned, it can be concluded that the retained austenite
retards the precipitation process or that there is no precipita-
tion of intermetalic compounds from retained austenite.
REFERENCES
[1] G. roberts, G. Krauss, r. Kennedy, tool steels, ASM International,
USA 1998, p. 1 - 97.
[2] m. Novosel, d. Krumes, Posebni čelici, strojarski fakultet, slavon-
ski Brod 1998, str. 375 - 393.
[3] i. Kladarić: doprinos proučavanju kinetike strukturnih pretvorbi
čelika maraging, doktorska disertacija, strojarski fakultet, slavon-
ski Brod 2002, str. 6 - 17 i 39 - 57.
[4] i. Kladarić, d. Krumes, r. marković, Proceedings, 1
st
International
conference on heat treatment and surface engineering of tools and
dies, Pula, B. smoljan, H. Jäger, V. leskovšek (editors), Croatian
society for Heat treatment and surface engineering (CsHtse),
zagreb 2005, p. 107 - 112.
List of symbols and abbreviation
ϑ
SA
- solution annealing temperature / °C
ϑ
A
- aging temperature / °C
t
SA
- solution annealing time / min
t
A
- aging time / min
A
s
- temperature of martensite-austenite transformation
/ °C
M
s
- temperature of austenite-martensite transformation
/ °C
HV1 - hardness value by Vickers method with load of 9,81
N
∆l

- contraction after solution annealing / mm
α

- average coeffcients of dilatation / K
–1
M
α

- average dilatation coeffcient of martensite / K
–1
A
α

- average dilatation coeffcient of austenite / K
–1
Z
α

- average dilatation coeffcient during heating / K
–1
%a - content of residual austenite / %
%m - content of martensite / %
l
0
- original sample length / mm
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1 900 MPa …¶‡‹ ‚ ˙¿ ¶¨ †»—‚ ˜ —˘
`ıæ–ƒ
1
, ´
1
, ” ˘ `œ
1
, `” ‰£—
1
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, ˛˜ »
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“ ¡¡“ : — ˘ ‡ » Rm ¡ 1 900 MPa ˜ ‚ı ·X=·<M·<©h÷´´≠Cí÷ ~.EX( < 200 mm) ‡‹ ‚ ˙¿ ¶¨ ´ ˚ˇ
˚– —§†»—‚ ,˝¤ „ —¿ ¨¨ ·ƒ „⁄ ¶ ¸ †»˝‹ ‡ • ˜ ‚ı ·X=·<M·<©h÷´`¨h∑¨+1©E≈1©í√©ƒ2©15XM÷X
4~h:,‰ł» †‰¯ »fl`¸ ”ˇ ‰‡ • ¡£‰Æ„ß– ˆ :¯ »fl‡ • ” ˆ ‰» ‚ ˙¿ ( Rm = 1 940 MPa) ¡¢‚ ¨˝ ( A KU2
= 55 J , KIC = 104 MPa ¡⁄ m) ˜ ´ ˚ˇ ˚– —§†»—‚ ¡£
„ … ·˚ : ´ ˚ˇ ˚– —§†» —‚ ; ˛ ‡ ˇ ; ‡‹ ‚ ˙¿ ¶¨
—˝…• ”¯ : TG142. 1 ¡¡ ¡¡ ¡¡ ˛˜ ˇ –Œ˚¶ ´º : A ¡¡ ¡¡ ¡¡ ˛˜ ´ – ”¯ : 1000·3738 (2008) 03·0048·04
A 1 900 MPa Grade Ultra·high Strength Stainless Steel
LIU Zhen·bao
1
, YANG Zhi·yong
1
, YONG Qi·long
1
, LIANGJian·xiong
1
,
SUN Yong·qing
1
, LI Wen·hui
1
, LU lun
2
(1. Cent ral Iron and Steel Research Instit ute , Beijing 100081 , China ;
2. Dongbei Special Steel Group , Fushun 113001 , China)
Abstract : A large size of super·high·st rengt h maraging stainless steel Cr·Ni·Co·Mo bar has been developed.
Effect s of heat t reat ment on mechanical properties of Cr·Ni·Co·Mo maraging stainless steel wit h eight different
component s were shudied. Through f urt her optimization of t he alloy composition : a high·st rengt h ( Rm = 1 940
MPa) , high·ductile ( A KU2 = 55 J and KIC = 104 MPa ¡⁄ m) maraging steel has been obtained. Good technological
properties of t his kind of steel make it suitable to be used as critical component s wit h high st rengt h and toughness
and sea water corrosion·resistantce. It also reveals broad application prospect s in aerospace , aviation and ot her
fields.
Key words : maraging stainless steel ; precipitation ; ult ra·high st rongt h
0 ¡¡ ¡¡
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†»—‚ Custom465 ¤ ß ,˘ ˙¿ ¶¨ · ‰ 1 800 MPa ,
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˚ ‚ ¨ ˘ :2007·04·25 ;—¶' ¨ ˘ :2007·09·13
»ø ‰ ˇ ˜¿ : „œ … ‚ ……˚ı — ¿ •¢ „ …˘»fi ˚ œ ˇ ˜¿ ( 863 -
2002AA305105)
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ª „»¨˝ —˜ ´ ˚ˇ ˚– —§†»—‚ ˜ —˘ ¡£
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—˝„⁄ ‡ —Ł“ ”ˇ Ł …˘`¸ ¸ ”ˇ ‰‡ • ,˝¤ „ ¯ »fl
ˆ ‰» —´—˝˜ < 200 mm ( †˜ ) ¡¢Rm ¡ 1 900
MPa ˜ ‡‹ ‚ ˙¿ ¶¨ ´ ˚ˇ ˚– —§†»—‚ ,Æ ‚ `¸ „œ˜ ´
˚ˇ ˚– —§†»—‚ ˜ ˙¿ ¶¨ …¶– ¡£
1 ¡¡ ˚ ø ˘ –‚ …˚ Ø •‰•¤
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‡ • ˚ Ø ‚ ,˘ »fl§ ‡ • …ß– 1 ,› ¶ ¸ ‡ • ˚
Ø ‚ ¨¨ ·ƒ „⁄ ¯ »fl ,¡ ¶¤ …—˜ ˜ ”ˇ ‰‡ • …¯
»fl˜ ¨¨ ·ƒ „⁄ (– 2) ,˝‹ ˚– ¶ ‚ˆ ”ˇ ‰˜ ‚ – “ ¸ ”‹
`¿ ¯ »fl ß ” ,† ˆ 3 000 kg ¿ ‚—ƒ ´fl + ¿ ”˜
´fl¨ `¶ , ” ˆ ‰‚ ·¿ ‰¶¨ ˜ ”ˇ ‰‡ • …ß– 3¡£
50 kg ´fl ¨ `¶ ˜ ‚ ¶§› 1 150 ¡ …¨¨ ”˝ ø ¨ »fl
·ƒ ” ¶˝ ‡ <15 mm ”˝ <50 mm¡¢‡⁄ ¶¨ ˛“ 50 mm ˜
¡⁄ 8 4 ¡⁄
32 3 ˘
2008 ˜Œ3 ´
»œ ¡¡ — ¡¡ „⁄ ¡¡ ‡ ¡¡ †˜ ¡¡ `ˇ
Material s ¡¡for ¡¡ Mechanical ¡¡ Engineering
Vol. 32 ¡¡ No. 3
Mar. 2008
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
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1 ¡¡ 50 kg ¿ ‚—ƒ ´fl¨ `¶ ¸ ˚ Ø ‚ »fl§ ‡ • ( ˚ `¿ • ˚ / %)
Tab. 1 ¡¡ Chemical composion of eight different test steel( mass/ %)
´fl”¯ C Si Mn S P Ni Cr Mo Co Ti V Fe
011
#
0. 030 0. 040 0. 028 0. 004 < 0. 005 4. 29 12. 46 5. 52 12. 95 - -
012
#
0. 031 0. 054 0. 028 0. 004 < 0. 005 4. 29 12. 56 5. 04 12. 90 0. 11 -
013
#
0. 039 0. 037 0. 022 0. 003 < 0. 005 4. 00 12. 02 3. 96 14. 60 0. 17 -
014
#
0. 096 0. 046 0. 022 0. 004 < 0. 005 4. 79 13. 86 4. 96 14. 40 - 0. 30
015
#
0. 140 0. 041 0. 027 0. 005 < 0. 005 4. 84 13. 93 4. 91 14. 34 - 0. 32
016
#
0. 097 0. 033 0. 027 0. 007 < 0. 005 4. 77 11. 93 4. 94 14. 36 - 0. 32
017
#
0. 180 1. 26 0. 041 0. 008 < 0. 005 3. 46 13. 10 2. 60 3. 82 - -
018
#
0. 220 1. 48 0. 044 0. 010 < 0. 005 3. 38 12. 86 2. 58 3. 45 - -
– 2 ¡¡ ¨¨ ·ƒ „⁄ ¶ ˚ Ø ‚ `ƒ § —˜ ˜ ˇ
Tab. 2 ¡¡ Effect of heat treatment on the mechanical properties of the steel
„⁄
011
#
012
#
013
#
017
#
018
#
Rm/ MPa Rp0. 2/ MPa A KU2/ J Rm/ MPa Rp0. 2/ MPa A KU2/ J Rm/ MPa Rp0. 2/ MPa A KU2/ J Rm/ MPa Rp0. 2/ MPa A KU2/ J Rm/ MPa Rp0. 2/ MPa A KU2/ J
1 1 690 1 440 67 1 540 1 300 106 1 560 1 360 16 1 680 1 460 17 1 750 1 390 20
2 1 780 1 510 70 1 630 1 340 95 1 770 1 650 37 1 570 1 370 23 1 540 1 400 18
3 1 650 1 350 76 1 640 1 400 82 1 540 1 320 30 1 820 1 360 40 1 850 1 410 18
4 1 710 1 390 60 1 730 1 460 70 1 730 1 600 23 1 650 1 350 20 1 670 1 400 26
5 1 640 1 440 72 1 600 1 420 80 1 580 1 410 18 1 870 1 240 46 1 930 1 210 42
6 1 820 1 440 60 1 850 1 560 64 1 740 1 610 24 1 670 1 290 37 1 690 1 300 29
– 3 ¡¡ 3 000 kg ¿ ‚—ƒ ´fl + ¿ ”˜ ´fl – `¶ ˜ <200 mm
†˜ ˜ »fl§ ‡ • ( ˚ `¿ • ˚ / %)
Tab. 3 ¡¡ Chemical composition of the optimizated
steel( mass/ %)
´fl”¯ C Mn Si Ni Cr Mo Al Ti Co Fe
031
#
0. 02¡«
0. 05
¡
0. 1
¡
0. 1
4. 0¡«
5. 0
11. 0¡«
14. 0
5. 0¡«
6. 0
¡
0. 2
0. 4¡«
0. 5
14. 0¡«
16. 0

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¡ ¡` 1 h + ‚” ˛´ ·ƒ + 550 ¡ ¡` 4 h ; (5) 1 050 ¡ ¡`
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‚ › „⁄ 5 ·ƒ ” ¿„ › ˙¿ ¶¨ • – ˛“ 1 870 , 1 930
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¡⁄ 9 4 ¡⁄
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© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
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( a) ¡¡ „ ¨ ¡¡ ¡¡ ¡¡ ( b) ¡¡ „ ¨ + ‚” ˛´ + 550 ¡ ˚– —§
˝…1 ¡¡ ¨¨ ·ƒ ¶ ˚ Ø ‚ † ¶¨ ( HRC) ˜ ˇ
Fig. 1 ¡¡ Effect of heat treatment on the hardness of the steel
( a) ¡¡the hardness of the steel after solution treatment at different
temperatures for 60 min ¡¡( b) ¡¡the hardness of the steel after solution
treatment and subzero treatment and aging at 550 ¡ for 240 min
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·ƒ ” ˚– —§˛´ ¶¨ ¶ 031
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Rm ¡¢R0. 2 ¸ ˚– —§ ˛´ ¶¨ ˜ … ,‚ ˜ ˙¿ ¶¨ ¸ fi …,`
535 ¡ ˚– —§” ‚ ˜ ˙¿ ¶¨ · ‰ • ( Rm = 1 940
MPa) ,fi ” ˙¿ ¶¨ ¿“ ˚…¸ ¯ ˚– —§˛´ ¶¨ ˜ ‚ ¶ł ‰˝ ¡£
‡ » „ƒ ¸ ¯ ˚– —§˛´ ¶¨ ˜ ‚ ‰¥ˇ´ ‰‰ ˝ ª
(535 ¡ ) ¨» ” ˇ ,·¸ ˚– ‡ » „ƒ A KU2 ˛“ 55 J ,¶ˇ ˆ
˚ ¸ı ´˚ Z ”˝ ‡⁄ ´˚ A – »fl„ ´ º ‡ » ˛ ˚ „ƒˇ ¸˘ ,
535 ¡ ˚– —§˚– ‰‰ ˝ ,fi ” ¸ ¯ ˚– —§˛´ ¶¨ ˜
‚ ¶ł »”´ ˇ ,` † ˆ ‚ˆ ˚– —§˛´ ¶¨ ˇ´ ‚ ˜ ˚ ˛´ ¶ˇ
` ¨˝ ¶¨ KIC ˛“ 104 MPa ¡⁄ m ¡£
˝…2 ¡¡ 1 050 ¡ „ ¨ …‚” ˛´ ·ƒ ” ˚– —§˛´ ¶¨
¶ 031
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‚ `ƒ § — ˜ ˜ ˇ
Fig. 2 ¡¡ Effects of aging temperature after 1 050 ¡ solution and
subzero treatment on the mechanical propertiesof 031
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steel
2. 3 ¡¡ ˚– —§˛´ ¶¨ ¶ ‚ ˇ ˛¢ Ø fl ˜ ˇ …˘ ˙¿ »fl»œ
˝…3 ¿ …ß,031
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‚ „ ¨ ” ˜ ˇ ˛¢ Ø fl ˛“ ‚ ˆ
¶¨ ˛» · ˜ ı ´ ˚ˇ Ø fl , ı ˜ ˘‰ø ¿ ¶¨ ˛“ 0. 2
ƒ m ,ˇ‚ —¡˜ ı …‚ ˆ ¶¨ ˜ ˛» · • †…˚˙ ˚„ ‚
—`…”ˆ ¨˝ —”˝ ‰ˇ‚ ˙¿ ¶¨ ˜ ˙ Æ ,˝‹ ˚– ‚ ˆ ¶¨ ˜ ˛»
· ˛“ ˚– —§˛ ‡ ˇ —˛”¸ Æ „' `¸ ‚ ¶ ˜ ‡¡ ¸ø ¡£¶ł 440 ¡
˚– —§” ‚ ˜ ˇ ˛¢ Ø fl —»ø– „ † †»‰˛ ‡ ˇ ,·¸ ˚–
‚ ˜ ˙¿ ¶¨ ‰ˇ˝ ¡£¶ 535 ,600 ¡ ˚– —§ˇ ˛¢ Ø fl –¨ ‰ˇ
¿ “ ,¸ ¯ ˚– —§˛´ ¶¨ ˜ ‚ , ˛ ‡ ˇ ˜ ‡ · ‰¥‡⁄
· , ˚˙ ‚ ˜ ˙¿ ¶¨ · ‰• ” ¸ ¯ ˚– —§˛´ ¶¨ ‚
¶ł ˇ´ ‰˜ › ¡£• ˛ ¨ˇ ˛“ ¸ ¯ ˚– —§˛´ ¶¨ ˜ ‚ ˛ ‡
ˇ …fl¡¢‡⁄ · , ˘˘ » `¸ º »ø …˜ „† ‚æ» º „† ‚æ„
ˇ ,· ¶ł ˚„ ‚ ˜ ˙¿ ¶¨ ˇ´ ‰¡£˝…3c — ‚ ˆ ¶¨ ˛» · ˜
ı ´ ˚ˇ ˇ ˆ ¢ • †…¯ · `¿ ˜ ˜ ˆ …¶˛ ‡ ˇ ¡£‚ø
˛˜ ˇ ‰Ø
[ 8 - 11 ]
, ‚ ”ˇ ‰‡‹ ‚ ˙¿ ¶¨ ´ ˚ˇ ˚– —§†»
—‚ —‡£…ߘ ˛ ‡ ˇ —˝ ˙ · Fe2 Mo —˝˜ Laves
ˇ ( hcp ª ‰Æ„„ ) Ni3 Ti , R ˇ ,ƒ ˇ ”˝ º · ˜ M2 C
¨ , —'ˇ‚ —¡˜ ˙¿ »flˇ · · Æ ‚ `¸ ‚ ˜ ˙¿ ¶¨ ¡£
3 ¡¡ ‰Æ¡¡ ´
—˘ ‡ „ƒ˜ 031
#
‚ <200 mm †˜ ˜ ¿„ › ˙¿ ¶¨
‚ · 1 940 MPa ,¶ˇ ` ¨˝ ¶¨ KIC ˛“ 104 MPa ¡⁄ m ¡£
†˛¿…˛˜ ˇ :
[ 1] ¡¡ Crawfird W M , Cont ractor G P. The effect s of st rengt hening
Be and Ti in maraging st ainless steel [J ] . J IPI ,1969 ,207(12) :
1642 - 1645.
[ 2] ¡¡˛” æ . ´ ˚ˇ ˚– —§†»—‚ [J ] . —´‰˚ †˜ `ˇ ,1972(4) :22 - 24.
[ 3] ¡¡ Imrie W H. Maraging steel in t he British aerospace indust ry
[J ] . Metal Forming ,1970 (1/ 2) :41 - 45.
[ 4] ¡¡ ‰“‰ , · , ·¤ , ¨ . ´ ˚ˇ ˚– —§†» —‚ ˜ •¢ „ ˇ ·
[J ] . ˚ ‚ ,2003 ,24(3) :1 - 5.
¡⁄ 0 5 ¡⁄
`ı æ –ƒ ,¨ :1 900 MPa …¶‡‹ ‚ ˙¿ ¶¨ †»—‚ ˜ —˘
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
Menu
( a) ¡¡ 1 050 ¡ „ ¨ ( b) ¡¡ 440 ¡ ˚– —§ ( c) ¡¡ 535 ¡ ˚– —§ ( d) ¡¡ 600 ¡ ˚– —§
˝…3 ¡¡ 031
#
‚ › †» ˝‹ ¨¨ ·ƒ ” ˜ TEM —˛ˆ†
Fig. 3 ¡¡ TEM images of 031
#
steel after heat treatment
( a) ¡¡ solution treatment at 1 050 ¡ ¡¡ ( b) ¡¡aging at 440 ¡ ¡¡ ( c) ¡¡aging at 535 ¡ ¡¡ ( d) ¡¡aging at 600 ¡
[ 5] ¡¡ Decker R F , Loreen S. Maraging Steel s·t he First 30 Years
[ C]/ / Wil son R K. Maraging Steel s·Recent Development and
Applications. Warrendale : TMSAIME , PA ,1988.
[ 6] ¡¡ ˇ¨ · ,»˘ „ »˝ . „œ˝ †»—‚ ˇ · …¶flˇ [J ] . „œ˝ ‰˚ †˜ `ˇ ,
1980 (5) :1 - 6.
[ 7] ¡¡ `ı æ –ƒ ,¸˛ ˛“ ¸‡ , ´ ,¨ . ˚– —§¶ ‡‹ ‚ ˙¿ ´ ˚ˇ ˚– —§†»—‚
Ø fl º —˜ ˜ ˇ [J ] . †˜ `ˇ ¨¨ ·ƒ § –¤ ,2005 ,26(4) :52 - 55.
[ 8] ¡¡ Honeycombe R W K. Metallurgical development s in high alloy
steel s[ J ] . Special Reprot 8b , The Iron and steel Inst , 1964
(54) :115 - 118.
[ 9] ¡¡ Versnyder F L , Beat tlejr H J . The Laves and chiphases in a
modified 12Cr stainless alloy [ J ] . Trans of t he ASM , 1955
(47) :211 - 230.
[ 10] ¡¡ Irvine K J . The development of high st rengt h steel [ J ] . J
Iron and Steel Inst ,1962 ,200 (10) :820 - 828.
[ 11] ¡¡ Kasak A , Chandhok C K , Dulis E J . Development of precipi·
tation hardening Cr·Mo·Co stainless st ell s [J ] . Trans ASM ,
1963 (56) :455 - 467.
(ˇ ‰ 47 ‡ )
( a) ¡¡ – ˆ
( b) ¡¡ ¶ˇ ˆ
˝…6 ¡¡ ‰Æ” SiC · SEM —˛ˆ†
Fig. 6 ¡¡ SEM images of the SiC ceramics
3 ¡¡ ‰Æ¡¡ ´
(1) SiC ˜ SPS ´ ˆ »fl„ ‡ ¿ ‚ø ˚– … ·=´
∂R~¯ =≈3¥$VhC•√=Ò4 ‚ ˙ł ……·•¯ ˘ł ¯ ˝ ˙ł ¡¢˘ł ‡
˚ ¸ı ˙ł ¡¢ ‰Æ˚ ¸ı ˙ł ¡¢ ‰Æ˝Œ‡ ˙ł ¡£
(2) … ‰Æ†˛ ˚ ˛“ 1 600 ¡ ¡¢50 MPa ¡¢5 min ,
‰Æˆ ¶¨ · 3. 27 g ¡⁄ cm
- 3
,´ ˆ ¶¨ · 99. 09 %¡£
(3) ‰Æˆ ‰˜ SiC · § `£ · —¡˛“ 1 ¡« 2
ƒ m ,¸ ˆ SPS ¿ ¸ ‰Æ‰ˇ”ˆ ¿ ˘ `¸ § `£ ˜ ‡⁄ · ,
¶ł ˙ § `£ · —¡ø ¨ ,˛ ‚ – § `£ ˜ ‡£‡⁄ · ¡£
†˛¿…˛˜ ˇ :
[ 1] ¡¡ Izhevskyi V A , Genova L A. Review article : silicon carbide.
st ruct ure , properties and processing[J ] . Ceramica ,2000 ,46 :4
- 14.
[ 2] ¡¡J ensen R J , Luecke W E , Padt ure N P. High temperat ure
properties of liquid phase sint eredƒ`·SiC[J ] . Material s Science
and Engineering A ,2000 ,282 (12) :109 - 114.
[ 3] ¡¡ Magnani G, Minoccari G L , Pilot tiL. Flexural st rengt h and
toughness of liquid phase sintered silicon carbide[J ] . Ceramics
International ,2000 ,26 (5) :495 - 500.
[ 4] ¡¡ She J H , Ueno K. Effect of additive cont ent on liquid·phase
sintering on silicon carbide ceramics[J ] . Mater Res Bull ,1999 ,
34(10/ 11) :1629 - 1636.
[ 5] ¡¡ Tamari N , Tanaka T , Tanaka K , et al . Effect of spark plasma
sintering on densification and mechanical properties of silicon
carbide [J ] . Journal of Ceramic Societ y of J apan ,1995 ,103(7) :
740 - 742.
[ 6] ¡¡ Francois G, Alexandre A. Densification of SiC by SPS·effect s
of time , temperat ure and pressure[J ] . Journal of t he Europe·
an Ceramic Societ y ,2007 ,27 (7) :2725 - 2728.
¡⁄ 1 5 ¡⁄
`ı æ –ƒ ,¨ :1 900 MPa …¶‡‹ ‚ ˙¿ ¶¨ †»—‚ ˜ —˘
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
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42 ¡¡ 3 ˘
¡¡ 2 0 0 7 ˜Œ 3 ´
‚ œ
Iron and Steel
¡¡ Vol. 42 , No. 3
March ¡¡ 2007
„ ¨ ·ƒ ¶ —´ —˝ ´ ˚ˇ ˚– —§ †» — ‚ `ƒ § — ˜ ˜ ˇ
`ı æ –ƒ
1
, ¡¡ ´
1
, ¡¡ ” ˘ `œ
1
, ¡¡ `” ‰£—
1
, ¡¡ ´‹ ¡¡ ´
2
(1. ‚ œ —¿ ” ‰Æ„„ †˜ `ˇ —¿ ¸ø , ––' 100081 ; ¡¡ 2. ¶«–– ˚ ‚ …fl˝¯ ……˚ı ——˜, ` ˜ ‚§ ¸‡ 113001)
“ ¡¡ “ : —¿ `¸ „ ¨ ·ƒ ¶ —´—˝Cr2Ni2Co2Mo ´ ˚ˇ ˚– —§†»—‚ `ƒ § —˜ ˜ ˇ ¡£‰Æ„ß– ˆ , ˝ 1050 ¡ „ ¨
·ƒ ˚– ‚ —· » —' ƒ ˇ ˛“ ˜ ‰˚ …ˇ ,¸ ˆ˙ †»‰ˇ ˘˘ » `¸ ‚ ˜ ¨˝ —,¶ł ˙ ˚„ ‚ ˚– —§·ƒ ” ˜ ˙¿ ¶¨
‰˝ `¸ 100 MPa ;› 1050 ¡ „ ¨ ·ƒ ” ‚ ˜ »ø Ø fl ˛“ ‚ ˆ ¶¨ ˛» · ˜ ı ´ ˚ˇ ,·¸ „ ¨ ‹ Ø fl › ˚˚ – ˚– —§·ƒ
¿ ˚„ ‚ ˜ ˙¿ ¶¨ · ‰1940 MPa ,˙ ˆ ‰º ˘ ‚ ¨˝ —˘¥ ¯ `…”ˆ ˜ ”ˇ `ƒ § —˜ ¡£
„ …·˚ : „ ¨ ·ƒ ; ƒ ˇ ; `ƒ § —˜
—˝…• ”¯ : TG142. 7 ¡¡ ¡¡ ˛˜ ˇ –Œ˚¶ ´º : A ¡¡ ¡¡ ˛˜ ´ – ”¯ : 04492749X(2007) 0320047205
Effect of Solution Treatment on Mechanical Properties
of a New Maraging Stainless Steel
L IU Zhen2bao
1
, ¡¡ YAN G Zhi2yong
1
, ¡¡ YON G Qi2long
1
, ¡¡L IAN GJian2xiong
1
, ¡¡LU2l un
2
(1. Instit ute for St ruct ural Materials , Cent ral Iron and Steel Research Instit ute , Beijing 100081 , China ;
2. Technical Center , Dongbei Special Steel Group , Fushun 113001 , Liaoning , China)
Abstract : The effect of solution t reat ment on mechanical properties of a new stainless steel , Cr2Ni2Co2Mo maraging
stainless steel was st udied. The result shows t hat t here are intermetallics in t he steel solution t reated at a tempera2
t ure lower t han 1050 ¡ wit hƒ phase as t he major phase. The intermetallics deteriorate toughness of t he steel ,and
t he st rengt h of t he steel is reduced by 100 MPa. There is lat hy martensite of high densit y dislocation in t he steel af2
ter 1 050 ¡ solid solution t reat ment for one hour. By proper aging t reat ment , t he st rengt h of t he steel may reach up
to 1 940 MPa ,wit h a good combination of st rengt h and toughness.
Key words : solution temperat ure ; ƒ phase ; mechanical properties
»ø‰ ˇ ˜¿ : „œ…‚ ……˚ı —¿ •¢ „ …˘»fi˚ œ ˇ ˜¿ (2002AA305105)
…‰Ø: `ı æ –ƒ (19772) , ˜—, †' ˚¿ œ ; ¡¡ ¡¡ E2mail : liuzhenbao1977 @yahoo. com. cn ; ¡¡ ¡¡ —¶' ¨ ˘ : 2006205222
¡¡ ¡¡ ´ ˚ˇ ˚– —§†» — ‚ ˜ ˙¿ ¨˝ »fl »œ˘ “ ¤ ´ ˚ˇ
ˇ – ˙¿ »fl ¡¢„ ¨ ˙¿ »fl ¡¢˚– —§˙¿ »fl … ¡ — —§§ `£ ¡–ˇ‚
»fl ˙¿ »fl ¨ ,˘ „ ¨ ·ƒ „⁄ ” · ‡ ¶¨ ˇ ¶¤`¸ §
`£ ˜ ——§‡ · …” ˘ ¿ ˜ †œœ ˜ ˚– —§˙¿ »fl—§„ß ,·
¶ł ˆ ˇ ˇ ‚ ˜ `ƒ § —˜ , ·¸ —¿ „ ¨ ·ƒ
„⁄ ¶ „ ¨ ‹ ˛¢ „ Ø fl …`ƒ § —˜ ˜ ˇ ˝ ˇ ˆ ˚fi
• “ ¡£–˚ —¿ `¸ » ———˘ ¿“ •¢ ˜ ˙¿ ¶¨ …¶–
1 900 MPa ˜ Cr2Ni2Co2Mo ´ ˚ˇ ˚– —§†»—‚ ˜
„ ¨ ·ƒ „⁄ ¶ ‚ ˜ „ ¨ ‹ ¡¢˚– —§‹ ˜ `ƒ § —˜ ˜
ˇ „ ´ ,· ¶ł ˛“ —´—˝´ ˚ˇ ˚– —§†»—‚ ˜ „⁄
»flœ †œ…ƒ ˆ Æ„' `¸ ¨¨ ·ƒ ˚ ¡£
1 ¡¡ ˚ Ø †˜ `ˇ ”˝ •‰•¤
˚ ؈ `ˇ †ˆ ¿ ‚—ƒ ´fl¨ `¶ (200 kg VIM)
+ ¿ ”˜ ´fl ¨ ˜ ¸« ¿ ¨ `¶ ,˚ Ø ‚ ˜ »fl§ ‡
• (˚ `¿ • ˚ , %) ˛“ : Cr 13. 0¡« 16. 5¡¢Ni 4. 0¡« 7. 5 ¡¢
Co 9. 5¡« 15. 0 ¡¢Mo 5. 0¡« 7. 5 ,˚˙ » ———˘ ¿“ •¢
˜ —´—˝‡‹ ˝ …´ ˚ˇ ˚– —§†»—‚ ¡£
‚ ¶§ › „ 1150 ¡ …¨¨ ”˝ ø ¨ »fl·ƒ ” ¶˝ ‡
<20 mm¡¢90 mm ¡` 90 mm ”˝ 55 mm ¡` 55 mm ˜ ˚
`ˇ ,†¢…„⁄ ‡ ˚ ø ,¨» ” ‰ł——„ ¨ ·ƒ ¡£„ ¨ ˛´ ¶¨ ˛“
830¡« 1100 ¡ ,„ ¨ ˚– …˛“ 60 min¡£„ ¨ ·ƒ ” ¿
¡£˛“ `¸ ˝Œ‡ ´ ˚ˇ ˇ – ,‰ł——‚” ˛´ ·ƒ ,·ƒ „⁄
˛“ - 73 ¡ –£˛´ 480 min († ˆ ˜ ‰Ø˚ ˛“ ‚ –ø + ˘ «
˜ –¥”˝ ¨ ” ) ¡£˚– —§‹ ˚ ø ˇ ˚ „ ¨ ·ƒ ˜ »ø
·¡ ˇ , 490¡« 600 ¡ •¶ ˛§ ˜ ¨ ˛´ ˚– —§240 min ,¿
¡£† ˆ APD210 X ˇ ˙ ¶ ˝ ˛´ „ ¨ ·ƒ ”
‚ —˜ ˛ ‡ ˇ ‰ł——`¸ …ł¶¤ ¡£
2 ¡¡ ˚ Ø ‰Æ„ß
2. 1 ¡¡ „ ¨ ˛´ ¶¨ ¶ „ ¨ ‹ ‚ `ƒ § —˜ ˜ ˇ
˝…1 ˛“ „ ¨ ˛´ ¶¨ ¶ ˚ Ø ‚ „ ¨ ‹ `ƒ § —˜ ˜
ˇ ,¿ ¿· ‡ ,˚ Ø ‚ ˜ ˙¿ ¶¨ ¸ ¯ „ ¨ ˛´ ¶¨ ˜ ‚ »ø
– ‡˚ `‹ —łˇ´ ‰˙ ˚˘ , ¿„ › ˙¿ ¶¨ 1145 MPa ‰`
1060 MPa ,¶ł ˙ • ˙¿ ¶¨ ˇ´ ‰˜ •ø ¶¨ –¨ ¿„ › ˙¿ ¶¨ ‚
· , 790 MPa ‰` 520 MPa ; ¸ —‚ –Œ( Z¡¢A)
Menu
42
¸ ¯ „ ¨ ˛´ ¶¨ ˜ ‚ ˇ¨ —¡•ø ˇ´ ‰¨» ” ‡ —ł · ,·
… 950 ¡ ‡ ˇ ¸ — ˜ ˝ ª ,¨˝ —‚ –Œ(‡ » „ƒ
AKU2
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¨˝ — ˜ ˝ ª ‡ ˇ 880 ¡ ¡£
2. 2 ¡¡ „ ¨ ˛´ ¶¨ ¶ ‚ „ ¨ ‹ Ø fl ˜ ˇ …˙¿ ¨˝ »fl»œ
• ˛
˛“ `¸ ‰ˇˇŒˇ‚ ‰˚˝ „ ¨ ˛´ ¶¨ ¶ ‚ ˜ „ ¨ ‹ `ƒ §
—˜ ˜ ˇ „ ´ ,ˆ ¤ ˆŁ „ † `¸ †»˝‹ ˛´ ¶¨ „ ¨
·ƒ ” ‚ ˜ Ø fl (˝…2) ¡£¿ ¿· ‡ ,› „ „ ¨ ·ƒ
” »ø Ø fl “ ˚˙ ı ´ ˚ˇ ¡£¸ ¯ „ ¨ ˛´ ¶¨ ˜
‚ ‚ ˜ § `£ · ,„ ¨ ˛´ ¶¨ 880 ¡ ` 1 100 ¡ ,
§ `£ ˘‰ø ‡ · 12ƒ m ` 60ƒ m ˇ ,¶ł ˙¿ ¶¨
1 140 MPa ‰` 1 060 MPa ,‚ø Hall2Petch › Ø „«
˚‰,§ `£ ‡ · · ˚˙ ‚ ˜ ˙¿ ¶¨ ¸ ¯ „ ¨ ˛´ ¶¨ ‚ ¶ł
ˇ´ ‰˜ » ‚ › ¡£
˝…1 ¡¡ „ ¨ ˛´ ¶¨ ¶ `ƒ § —˜ ˜ ˇ
Fig. 1 ¡¡ Effect of solution temperature on mechanical
properties
¡¡ ¡¡ ˝…2 (a) ¿ •¢ ˇ ,› 880 ¡ „ ¨ ·ƒ ” ‚ —
· · `¿ ˜ ˛ ‡ ˇ ¡£› 1040 ¡ „ ¨ ·ƒ ” ‚ —†
· ˛ ‡ ˇ (˝…2 ( b) ) , « ˘ ˚ `¿ ˚fi • ˇ¡ ¡£
1050 ¡ ˇ ˜ ˛´ ¶¨ „ ¨ ·ƒ ˜ ˚ ø — ¿· †»‰˛
‡ ˇ ¡£¸ ˆ ˛ ‡ ˇ ¸ ¯ „ ¨ ˛´ ¶¨ ˜ ‚ ¶ł †»¶ˇ ¨ ‰
ˇß ˚§ † ˚˙ ‚ ˜ ˙¿ ¶¨ ‡ —łˇ´ ‰˜ “ › ¡£
› • ˛ , ˛ ‡ ˇ ˚˙ ƒ ˇ ˛“ ˜ ‰˚ …
ˇ ¡£˝…3 ˛“ › 880 ¡ „ ¨ ·ƒ ” ˚ Ø ‚ —˛ ‡ ˇ ›
X ˇ • ˛ ˜ ‰Æ„ß ¡£ ‰ı …: 3. 6 %ZnCl2 ,
5 %˛ ¸Æ,1 %˜ß ˆ˚ ¸Æ…·…¨ ” , ` ˆ ¶¨ ˛“ 0. 05 A/
cm
2
,˛´ ¶¨ ˛“ 5¡« - 10 ¡ ¡£› „ • ˛ ˝…3 ¿ “ ,˛ ‡
ˇ ˚˙ ƒ ˇ ˛“ ˜ ‰˚ …ˇ ,ƒ ˇ ˜ § ˆ … ”˝ ˙¿
¶¨ …ß– 1 ¡£
˝…4 ˛“ „ † ‰˜ § ‰˛ ‡ ˜ ƒ ˇ …˘
ª ¡£· ˝…—¿ ¿· ‡ ,ƒ ˇ ˜ ˘‰ø ‡ · ‰ˇ· ,˙ ˇ § ˜
œ ‡⁄ ,ˇ ˘˘ » `¸ »ø ˜ `‹ —ł—, …´ ‚ ˜ ¨˝ —ˇ´
‰, † ˙¡ ”ˆ ¸ ˆ `¸ 880 ¡ „ ¨ ” ‚ ˜ ‡ » „ƒ‰ˇ˝
˜ › (˝…1) ¡£
˝…5 ˛“ „ † ‰˜ ` » —˛ˆ† ˜ ƒ ˇ , ‡¡ ˇæ—˜
ƒ ˇ ˇ —•¯ · ˜ ı ˛˘ , ı ˛˘ ˜ ‡ —· ‰¸ ¡£
˝¤ „ ˇ ˚ ˜ •‰•¤ ¨• ¶¤`¸ 880 ¡ „ ¨ ·ƒ ” ‚ —
˜ ‰˚ …ˇ ˛“ ƒ ˇ ,—˛˜ ˇ –¤ `¸ ‚ ”ˇ ‰‚ —
`‰ ƒ ˇ ˜ —˝Ø ‡ ˚‰• – ˛“ Fe35 Ni3 Cr13 Ti7
[ 1 ]
”˝
Fe27 Ni8 Cr13 Ti4. 5 Mo0. 55
[ 2 ]
, †¢¸ ƒ ˇ ˜ œ ‡ †»‰»Æ
ˇ ‰˝ ‚ ˜ ¨˝ —¶ł ˙ »„ »Æ‰˝ ˚– —§” ‚ ˜ ˙¿ ¶¨ ¡£
‚ø – ˚ Ø ‰Æ„ß¿ “ ‚ 880 ¡ „ ¨ ·ƒ ” œ ‡ ƒ
ˇ ˚˙ ·¸ ‚ ¨˝ —‰˝ ˜ “ › ¡£
(a) 880 ¡ ; ¡¡ ( b) 1 040 ¡ ; ¡¡ (c) 1050 ¡ ; ¡¡ (d) 1 100 ¡
˝…2 ¡¡ ˚ Ø ‚ › †»˝‹ ˛´ ¶¨ „ ¨ ·ƒ 60 min ” ˜ Ø fl ( SEM)
Fig. 2 Microstructure of steel after solution treatment at different temperatures for 60 min , SEM
¡⁄ 8 4 ¡⁄
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3 ˘ `ı æ –ƒ¨ :„ ¨ ·ƒ ¶ —´—˝´ ˚ˇ ˚– —§†»—‚ `ƒ § —˜ ˜ ˇ
˝…3 ¡¡ 880 ¡ ¡` 60 min „ ¨ ·ƒ ” ‚ —ƒ ˇ ˜ X ˇ
• ˛
Fig. 3 ¡¡ X2ray phase analysis of ƒ phase in steel after 880
¡ solution treatment for 60 min
– 1 ¡¡ ‚ —ƒ ˇ ˜ § ˆ ‚ ˚
Table 1 ¡¡ Interplaner spacings of ƒ phase in test steel
˚ ø ”¯ ( hkl)
I
I 0
d/ nm
1 321 15 0. 237 8
2 330 100 0. 209 8
3 332 24 0. 189 7
4 552 22 0. 121 1
¡¡ ¡¡ ¢ :ƒ ˇ ˛“ —˜`¢ •‰‰Æ„„ , a0 = 0. 890 nm¡£
2. 3 ¡¡ „ ¨ ˛´ ¶¨ ¶ ‚ ˚– —§‹ ˜ `ƒ § —˜ ˜ ˇ
—¿ `¸ `‰ †»˝‹ ˜ „ ¨ ·ƒ „⁄ (880 ¡ „ ¨
·ƒ + ‚” ˛´ ·ƒ , ˇ´ …‡˘ „⁄ 1 ; 1050 ¡ „ ¨ ·ƒ
+ ‚” ˛´ ·ƒ , ˇ´ …‡˘ „⁄ 2) ¶ › ˚– —§·ƒ ˜ ‚
˜ `ƒ § —˜ ˜ ˇ ¡£· ˝…6 ¿ ¿· ‡ ‚ ˜ ˙¿ ¶¨ ¸ ¯
(a) ƒ ˇ ˜ BF ; ¡¡ ( b) ƒ ˇ ˜ DF ; ¡¡ (c) ¡ ˙ł ˘ ; ¡¡ (d) ª ˜ –Œ¶¤
˝…4 ¡¡ 880 ¡ ¡` 60 min „ ¨ ·ƒ ” ‚ —˜ ƒ ˇ ( TEM)
Fig. 4 ¡¡ƒ phase in steel after 880 ¡ solution treatment for 60 min , TEM
(a) ƒ ˇ ˜ DF …¡ ˙ł ˘ ; ¡¡ ( b) ª ˜ –Œ¶¤
˝…5 ¡¡ 880 ¡ ¡` 60 min „ ¨ ·ƒ ” ‚ —˜ ƒ ˇ ( TEM)
Fig. 5 ¡¡ƒ phase in steel after 880 ¡ solution treatment for 60 min , TEM
¡⁄ 9 4 ¡⁄
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42
˝…6 ¡¡ ˚– —§˛´ ¶¨ ¶ `ƒ § —˜ ˜ ˇ
Fig. 6 ¡¡ Effect of aging temperature on mechanical prop2
erties of steel
˚– —§˛´ ¶¨ ˜ ‚ ˇ¨ ˇ ¨» ” ‰¥ˇ´ ‰ ¡£ „ ¨
˛´ ¶¨ †» ˝‹ ,· ‰˙¿ ¶¨ • ˜ ˛´ ¶¨ † †»˝‹ ¡£› „⁄ 1
·ƒ ” ‚ ˜ ˙¿ ¶¨ 550 ¡ ¡` 240 min · ‰• 1 840
MPa ,¶ł › „⁄ 2 ·ƒ ” ‚ ˜ ˙¿ ¶¨ 530 ¡ ¡` 240
min · ‰• 1 940 MPa ¡£¨˝ —‚ –Œ‡ » „ƒ ¸ ¯ ˚–
—§˛´ ¶¨ ˜ ‚ ˇ¨ »” ´ ˇ´ ‰¨» ” ‰¥ˇ , ˙ ø
530 ¡ ˚– —§” ‰‰ ˝ ¡£› „⁄ 2 + ˚– —§·ƒ ” ‚
˜ ‡ » „ƒø ‚ „⁄ 1 + ˚– —§·ƒ ,› „⁄ 1 + 550
¡ ¡` 240 min ·ƒ ” ¸ ˙¿ ¶¨ ‰ˇ‚ « ‡ » „ƒ ‰˛“ 24
J ,¶ł › „⁄ 2 + 530 ¡ ¡` 240 min ·ƒ ” ˜ ‡ » „ƒ
· ‰ 59 J ¡£¸ —‚ –Œ( A ¡¢Z) º ‡ » „ƒ˜ – »fl„ ´ ˇ
‰¡£ ˆ » Æ ˜ ˚˙ ,„⁄ 1 + ˚– —§·ƒ ” ‚ ˜ ¶ˇ ˆ
˚ ¸ı ´˚ ”˝ ‡⁄ ´˚ ø ˝ „⁄ 2 + ˚– —§·ƒ ¡£ ·¸ ¿
…ß,› 1 050 ¡ ¡` 60 min + - 73 ¡ ¡` 480 min + 530
¡ ¡` 240 min „⁄ ·ƒ ” ,˚ Ø ‚ —‚ ˙¿ ¶¨ ”˝ ‚
¨˝ —, ”ˇ `ƒ § —˜ ˘¥ ¯ `…”ˆ ¡£
2. 4 ¡¡ „ ¨ ˛´ ¶¨ ¶ ‚ ˚– —§‹ Ø fl ˜ ˇ …˙¿ ¨˝ »fl»œ
• ˛
˝…7 ( a) ¡¢( b) • – ˛“ › „⁄ 2 + 530 ¡ ¡` 240
min¡¢„⁄ 1 + 550 ¡ ¡` 240 min ·ƒ ” ,‚ ˜ ˛¢ „ Ø
fl ˜ TEM ˇæ ¡£· ˝…7 (a) ¿ ¿· ‡ ,› „⁄ 2 + ˚–
—§·ƒ ” ,‚ ˆ ¶¨ ˛» · ˜ ı ´ ˚ˇ ˇ ˆ ¢ • †…¯
· `¿ ˜ ˜ ˆ …¶˛ ‡ ˇ ¡£‚ø · `¿ ˛˜ ˇ ˜ ‰Ø
[ 3¡« 7 ]
,
‚ ”ˇ ‰‚ ˙¿ ¶¨ ´ ˚ˇ ˚– —§†»—‚ —‡£…ߘ ˛ ‡ ˇ
—˝ ˙ · Fe2 Mo —˝˜ Laves ˇ ( hcp ª ‰Æ„„ ) ”˝ º
· ˜ M2 C ¨ , —'ˇ‚ —¡˜ ˙¿ »flˇ · · Æ‚ `¸ ‚ ˜
˙¿ ¶¨ ¡£
· ˝…7 ( b) ¿ ¿· ‡ ,¸ ¨» ˝‹ ø »ø ˇ œ ‡ `¸
· `¿ ˇ‚ —¡˜ ˛ ‡ ˇ ,« ƒ ˇ ˛“ ˜ ‰˚ …ˇ
˜ · ,˚„ ‚ —ˇ‚ —¡˙¿ »flˇ ˜ » • ˚ …ı , ·¸ ¿
…ß, ƒ ˇ ˛“ ˜ ‰˚ …ˇ ¶Æ `¸ · `¿ ˜ ˙¿ »fl“ ¸
(¨ Mo ¡¢Co) , … `¸ ‚ —˜ ˆ …¶˙¿ »flˇ ˜ » •
˚ ,· ¶ł ˇ `¸ ‚ ˜ ˚– —§˙¿ »fl—§„ß , ˛“ ƒ ˇ ˜
· ,˚„ ‚ ˜ ¨˝ ¡¢¸ —ø ˇ´ ‰(˝…6) , ¶ł ¸ø —¿
˜ ˚ Ø ‚ ˜ ‡ • •¶ ˛§ ˜ , ˝ ˛´ „ ¨ ·ƒ ˚– · ˜
ƒ ˇ ˛“ ˜ ‰˚ …ˇ †»« »Æ‰˝ ‚ ˜ ˙¿ ¶¨ ,¶ł ˙
»„»Æ‰˝ ‚ ˜ ¨˝ ¡¢¸ —¡£
3 ¡¡ ´
˛´ ¶¨˝ 1 050 ¡ ¡¢60 min ˜ „ ¨ ·ƒ ” ,‚
—· ƒ ˇ ˛“ ˜ ‰˚ …ˇ ,¨ ˘ ˚˙ 880 ¡ ¡`
60 min ˜ „ ¨ ·ƒ ” ,‰˚ …ˇ ˜ ˚ `¿ ¶ ,·¸ ˚–
‚ ˜ ¨˝ ¡¢¸ —‚ –Œø ” ˝ , – ˚˙ ‡ » ¡£ —'‰˚
…ˇ § ‰ˇ œ ‡⁄ ,‡ · ‰ˇ· ,˙ ˛ „ ´ ˇ § ˜
‡⁄ · ,»Æˇ ł ‰˝ ‚ ˜ ¨˝ —,¸ ˆ˙ ˜ · …´ ‚ —
(a) „⁄ 2 + 530 ¡ ¡` 240 min ·ƒ ” »ø ˜ BF ; ¡¡ ( b) „⁄ 1 + 550 ¡ ¡` 240 min ·ƒ ” »ø ˜ BF
˝…7 ¡¡ › „ ¨ ·ƒ ” • ˚– —§˚– ‚ ˜ Ø fl ˜ TEM ˇæ
Fig. 7 ¡¡ Microstructure of steel at aging peak after solution treatment , TEM
¡⁄ 0 5 ¡⁄
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3 ˘ `ı æ –ƒ¨ :„ ¨ ·ƒ ¶ —´—˝´ ˚ˇ ˚– —§†»—‚ `ƒ § —˜ ˜ ˇ
˙¿ »fl“ ¸ ˜ ”‹ `¿ ˇ´ ‰ ,˚„ ˚– —§˚– œ ‡ ˜ ˜ ˆ …¶˙¿ »fl
ˇ ˜ » • ˚ ˇ´ ‰, · ¶ł ‰˝ `¸ ‚ ˜ ˙¿ ¶¨ ; ›
1 050 ¡ ¡` 60 min „ ¨ ” ,‚ ˜ »ø Ø fl ø ˛“ ‚ ˛»
· ˆ ¶¨ ˜ ı ´ ˚ˇ ,ˆ» —‰˚ …ˇ ,·¸ ˚– ‚ ˜ ¨˝ ¡¢
¸ — ”ˆ ,› „ ‚” ˛´ ·ƒ + ˚– —§·ƒ ” ‚ —˛ ‡ ·
`¿ ˆ ¢ ˜ ˜ ˆ …¶˙¿ »flˇ ,˛ ‡ ˇ · · Æ ‚ `¸ ‚ ˜ ˙¿
¶¨ ¡£› ˇ ˚ • ˛ ¿ “ , 1 050 ¡ ¡` 60 min + - 73 ¡
¡` 480 min + 530 ¡ ¡` 240 min ˚˙ ˚ Ø ‚ ”ˆ ˜ ¨¨
·ƒ „⁄ ¡£
4 ¡¡ ‰Æ´
(1) › 1 050 ¡ ¡` 60 min „ ¨ ·ƒ ” ,‚ ˜ ˛¢ „
Ø fl ‰Æ„„ ˛“ ‚ ˆ ¶¨ ˛» · ˜ ı ´ ˚ˇ ,·¸ ˚– ”ˇ ‰“
¸ ‡ • „ ¨ ‚ — ,˛“ ˚– —§˙¿ »flÆ „' `¸ – “ ˜ …
–‚ ¡£
(2) › 880 ¡ ¡` 60 min „ ¨ ·ƒ ” ,‚ —·
· `¿ ˜ ƒ ˇ ˛“ ˜ ‰˚ …ˇ ,¸ ˆ˙ § ‰ˇ ˜ ‡
· ‰ˇ· ¡¢—˛· †»„ ,ˇ ‰˝ `¸ ‚ ˜ ¨˝ ¡¢¸ —¡£
(3) › 1 050 ¡ ¡` 60 min + - 73 ¡ ¡` 480 min +
530 ¡ ¡` 240 min ·ƒ ” ,‚ —œ ‡ · `¿ ˆ ¢ ˜ ˜ ˆ
…¶˙¿ »flˇ ,·¸ ˚– ‚ ˜ ˙¿ ¶¨ · ‰`¸ 1 940 MPa ,˙ –£‡
`…”ˆ ˜ ¨˝ —; ¶ł › 880 ¡ ¡` 60 min + - 73 ¡ ¡` 480
min + 550 ¡ ¡` 240 min ·ƒ ” ,¸ ¨» ‚ ˜ ˙¿ ¶¨ ‰ˇ‚
(1 840 MPa) ,« ˚˙ ¨˝ ¡¢¸ —‚ –Œ” ˝ ,” ˜ ƒ ˆ „⁄
‡ ˇ ¡£
†˛¿…˛˜ ˇ :
[ 1] ¡¡ Hughes H , Llewelyn D T. ƒ Phase in t he Fe2Cr2Ni2Ti Syst em
[J ] . J Iron Steel Inst , 1959 ,192 (6) :170.
[ 2 ] ¡¡ Beet t e J r H J . Int ragranular Precipitation of Int ermetallic
Compounds in Complex Austenitic Alloys [ J ] . Trans AIME ,
1961 ,221 (1) :28235.
[ 3] ¡¡ Irvine KJ . The Development of High St rengt h Steel [J ] . J I2
ron and Steel Inst ,1962 ,200(10) :8202828.
[ 4] ¡¡ Kasak A , Chandhok C K, Dulis E J . Development of Precipi2
tation Hardening Cr2Mo2Co St ainless Steel s [J ] . Trans ASM ,
1963 ,56 :4552467.
[ 5] ¡¡ æ , ·” , ¡¡ ,¨ . » ‡‹ ‚ ˙¿ ¶¨ †»—‡ ´ ‚ ˙¿ »flˇ
—¿ [J ] . ”‰¿ †˜ `ˇ § –¤ ,2003 ,23 (1) : 126. ( ZHAO Zhen2ye ,
LI Chun2zhi , LI2Zhi ,et al . St udy on t he St rengt hening Phase
in a Ult ra2High St rengt h Stainless Gear St eel [J ] . Journal of
Aeronautical Material s ,2003 ,23 (1) : 126. )
[ 6] ¡¡ Honeycombe R W K. Metallurgical Development s in High Al2
loy Steel s[J ] . The Iron and Steel Inst ,1964 , Special Report 8b.
[ 7] ¡¡ Versnyder F L , Beat tle J r H J . The Laves and Chiphases in a
Modified 12Cr Stainless Alloy [ J ] . Trans of t he ASM , 1955 ,
47 :2112230.
¡⁄ 1 5 ¡⁄
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%1 5 % %4 # ! ! & E # F % Vol. 15, No. 4
1 9 7 9 q 12 A ACTA METALLURGICA SINICA December 1 9 7 9
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M e n u
PHASE TRANSFORMATION AND MECHANICAL PROPERTIES
OF MARAGING STAINLESS STEELS
Li Jianchun, Gao Anjuan and Wang Zhanyi
(Central South Institute of Mining and Metallurgy)
Abstract
The volume fractions of ~lustenite have been determined on two maraging
stainless steels with respect to tempering temperature and time or quenching tem-
perature. When the specimens were quenched from 850°C and tempered under dif-
ferent temperatures for 4h, the reverted austenite began to appear L; a tempering
temperature of about 550°C, reached its peak value of ?C% vc-ki l ~e fraction at
about 610°C and disappeared over 700°C. Unc'er reriain detnitc tercpering temper-
ature their volume fractions were increa~ct! ss prolon~e:r,r, the tempering time.
And the process seems to be of dif:usian cor.tro1lir.k. The minimum volume frac-
tion of austenite, being rlecr ;:ero, r ~sr ; ~esulted by being quenched at 1000 or
950°C under SGrrce tr91~1peri;~g i:mperature of 580°C for 4h.
T::r efl'cc'. 0,' dizerent heat treatment on the microstrain Aa/a of the steels,
closely rcidtol to phase transformation process of MSA, has also been investigated
by means of X-ray diffraction. The presence of austenite at any 10% would cause
loss of strength of both steels about 10 kg/mm2, however, their toughness might
be actually improved by these softer austenites formed along the boundaries of
lath martensite. In view of combining both strength and toughness of the steels
the proper heat treatment process to form 5-10% stable reverted austenite would
perhaps be desirable.
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29 ¡¡ 4˘
2 0 0 8 ˜Œ ¡¡ 8 ´
†˜ ¡¡ `ˇ ¡¡ ¨¨ ¡¡ ·ƒ ¡¡ ¡¡ § ¡¡ –¤
TRANSACTIONS OF MATERIALS AND HEAT TREATMENT
Vol . 2 9 ¡¡ No . 4
August 2008
´ ˚ˇ ˚– —§ †» — ‚ ˜ •¢ „
´ , ¡¡ `ı æ –ƒ , ¡¡ `” ‰£—, ¡¡ ¸ ˙ , ¡¡ ˛˜ »
(‚ œ —¿ ” ,––' ¡¡ 100081)
“ ¡¡“ : —˚ `¸ ´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „ œ ˚• º ˇ · ,†¢ ‰Æ`¸ ‚ˆ ‚ ˜ ‡ • ¡¢—˜ ”˝ ˙¿ ¨˝ »fl»œ ¨ •‰ˆ ˜
ª ¡£´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „ ˙ ˚˘ ˚˙ † ˆ ‡‹ ‚ ‰» ¶¨ ([ H] + [O] + [N] + [ S] + [ P] ¡ 40 ¡` 10
- 6
(ppm) ) ˜ ¿
¨ `¶ …¨« ` ‡ Ø fl ˇ‚ »fl…‡ • ø ¨ »fl¿ ˘ ¨ ……˚ı ,—˘ ‚ ˙¿ ¡¢‚ ¨˝ ¡¢ —¯ `… ”ˇ —˜ ˜ ´ ˚ˇ ˚– —§†»—‚ ¡£
„ …·˚ :´ ˚ˇ ˚– —§†»—‚ ; ¡¡ ”ˇ ‰“ ¸ ; ¡¡ `ƒ § —˜
—˝…• ”¯ : TG1421 ¡¡ ¡¡ ¡¡ ˛˜ ˇ –Œ˚¶ ´º : A ¡¡ ¡¡ ¡¡ ˛˜ ´ – ”¯ : 1009·6264(2008) 04·0001·07
Development of maraging stainless steel
YANG Zhi·yong , ¡¡LIU Zhen·bao , ¡¡LIANGJian·xiong , ¡¡ SUN Yong·qing , ¡¡LI Wen·hui
( Institute for Structural Materials Central Iron and Steel Research Institute , Beijing 100081 ,China)
Abstract : The development and state·of·the·art of maraging stainless steel , including its chemical composition , properties and the mechanism of
strengthening and toughening is reviewed. The developing trend of application of super pure vacuum melting technology( [ H] + [O] + [N] + [ S]
+ [ P] ¡ 40 ¡` 10
- 6
(ppm) ) and the controlling of extra·fine grain homogenization structure in whole fabricating process is emphasized.
Key words :maraging stainless steel ; alloy element ; mechanical property
˚ ‚ ¨ ˘ : ¡¡2007·07·09 ; ¡¡ —¶' ¨ ˘ : ¡¡2008·06·10
»ø‰ˇ ˜¿ : ¡¡ „œ…‚ ……˚ı —¿ •¢ „ …˘»fi(863·2002AA305105)
…‰Ø: ¡¡ ´ (1959 ¡“) ,˜—,‚ œ —¿ ” ‰Æ„„ ¸ø ‰˚ , “ ·
˚´ ‡‹ ‚ ˙¿ ¶¨ †» —‚ ` — •¢ „⁄ , » : 010·62183324 , E·mail :
yangzhiyong @nercast . com¡£
¡¡ ¡¡ 20 ˚ …˝60 ˜Œ·œ” ˘ ˛˚ ˚ ˜ ´ ˚ˇ ˚– —§†»—‚
˚˙ » —´—˝˜ ‚ ˙¿ ¶¨ †»—‚ ,¸ ˜ •¢ „ » •‰ˆ ˚˙
‡` † »fl†»—‚ ˜ ˜‡ —'—˜ ‰ˇ† » ¨¨ ·ƒ „⁄ ‚·
¶ł ‰· ‚˜ ‰ł,` » •‰ˆ ˚˙ ˚ ‰`¸ ´ ˚ˇ ˚– —§‚ ”ˇ ‰»fl
˜ › …`…”ˆ ˜ ”ˇ —˜ ˜ ˘ •¢ ¡£´ ˚ˇ ˚– —§†»
—‚ †»‰ —´ ˚ˇ ˚– —§‚ ¯ `…˜ ˙¿ ¡¢¨˝ —˜ ,»„
—†»—‚ ‰ˇ”ˆ ˜ ˜˝ ‚fl ˚· —˜ ,˝‹ ˚– ,¸ ˜ …„⁄ —˜ ”˝
”‚ ‰—˜ ”ˆ ¡¢fl —¯ ¡¢¨¨ ˛¨ ¶¤—`…”ˆ ,¨¨ ·ƒ „⁄ …
¥ , ¶ł „œ˜ ˝ ˆ ‰`¸ „ª •” ˜ ƒ ˆ ”˝ •¢ „ , ‡ ˛“
‚ ˙¿ ¶¨ †»—‚ ˇ `—— —•¢ „ ˙ ˝ ˜ ‚
[1 ,2]
¡£ ˛ „œ
· ˇ ‚ ˚ …˝ 70 ˜Œ·œ¿“ ˚…—¿ ,†¢˙ › —˘ ‡ `¸ ˙¿
¶¨ …¶– ˛“ 1200¡¢1400¡¢1600MPa ˜ ´ ˚ˇ ˚– —§†»—‚ ,
¸ ‚ ˜ ˙¿ ¶¨ ,´œ ˜ †»——”˝ `…”ˆ ˜ ”ˇ —˜ ‚
¸ ‡ ˛“ • »œ¡¢» …¡¢…fl ¿˙ ¨ „ …Ł –‚ ˜ ‡—`ƒ ˜˝
˚· (» —˛´ ) †¿…˜ ˚ ¡ †˜ `ˇ
[3·7]
¡£
1 ¡¡ ´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „ œ ˚•
20 ˚ …˝60 ˜Œ·œ‡ı ,„œ…˚˜ł „«¸ •¢ – ´ ˚ˇ ˚– —§‚

[8 ,9]
,˛“ •¢ „ ‚ ˙¿ ¶¨ ´ ˚ˇ †»—‚ ¨º `¸ ´ ˚ˇ ˚– —§
˙¿ »fl » —´‚¯ ˜ ,· ‰ł`¸ ´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „ ¡£
1961 ˜Œˆ „œCarpenter Technology „«¸ —˘ `¸ » ‚ ”‹
Co ˜ Pyromet X·12 ´ ˚ˇ ˚– —§†»—‚ ,” •¢ – `¸ †»
”‹ Co ˜ Custom450¡¢455 ; 1967¡¢1973 ˜Œˇ¨ ” •¢ – `¸
Pyromet X·15¡¢Pyromet X·2 ,·¸ …ˆ „œ» —'„«¸ ˇ¨ ” •¢ –
`¸ AM363¡¢Almar362¡¢In736¡¢PH13·8Mo ¡¢Unimar CR ¨ ;
Martin ¨ ¨¸ • – 1997 ˜Œ ”˝ 2003 ˜Œ »æ ˆ `¸
Custom465
[10]
”˝ Custom475
[11]
˜ •¢ ˆ ¤ ß ¡£ •¤ „œ — ‚ ˙¿
¶¨ †» — ‚ –Œ … ( 7 ‚ ‚ ”¯ ) , ·¸ ˝ »„ — ¿ `¸
Cr12Ni7Mo2TiAl ¡¢0Cr14Ni4Cu3Mo¡¢0Cr14Ni4Cu3 ¨ ‚ ”¯ ¡£
¢ „œ—•¢ ˜ ‚ — FV448¡¢520¡¢520 (B) ¡¢520 ( S) ¡¢535¡¢
566¡¢ D70 … SΠSAV ¡¢SΠSJ2 ,12Cr·8Ni·Be ¨
[12]
¡£ ´ „œ
1967¡¢1971 ˜Œ—˘ •¢ – `¸ Ultrafort401¡¢402 ¨ ‚
[13]
¡£
˙ ¸ `“ ‡ •´ ˘ ¡¢‚˜ ‰ł ˆ „œ ‚ ”¯ ˝ ,»„¶ `¢ —¿ `¸ » ˇ `—
—´ ‚ ”¯ , ‡£ …ߘ ‚ — 0§•15 §fl8 § ¡¢0§•17 §fl5 §fi3¡¢
1§•15 §fl4§¡§fi3¡¢07§•16 §fl6 ¨ …· `¿ ”‹ ‚ ”¯ , ¨
00§•12§‹14 §fl5 §fi5§·¡¢00§•14§‹14 §fl4 §fi3§· ¨ ¡£2002 ˜Œˆ „œ
QuesTek —´……˚ı —ˇ ¨˛ „«¸ ‡—£ ˆ „œ• †¿‰´ »• ‡
—¿ º •¢ „ …˘»fi (SERDP) ˛ ¨ • „ ˇ ˜¿ ,‚ˆ ˇ ˜¿ “ ˙
Ł …˘—´—˝• »œ˘ ´ …†˜ `ˇ , …·´ ˚ˇ ˚– —§†» —‚
FerriumS53 ,‚ˆ †˜ `ˇ 2006 ˜Œ —˘ ‡ „ƒ ,FerriumS53 ˙¿
¶¨ … 1980MPa , K
IC
· ‰ 80MPa m ˇ
[14]
¡£
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
Menu
20 ˚ …˝70 ˜Œ·œ¿“ ˚…´ ˚ˇ ˚– —§†»—‚
˜ — ˘ „⁄
[5]
, — ˘ ˜ —˝ ‚ —
00Cr13Ni8Mo2NbTi
[7]
, 00Cr12Ni8Cu2AlNb , 00Cr10Ni10·
Mo2Ti1
[15]
¨ 10 ¡£2002 ` 2005 ˜Œ‚ œ —¿ ”
‡ „ƒŁ …˘†¢—˘ ‡ —´—˝˜ ‡‹ ‚ ¨˝ —º ‡‹ ‚ ˙¿ ¶¨ ´ ˚ˇ
˚– —§†»—‚ ,‚ˆ ‚ ˚˙ ˛ „œ —•¢ †¢ — “ ˚¶
†œ¨¤ ˜ Cr·Ni·Co·Mo ˇ ´ ˚ˇ ˚– —§†»—‚ ,˘ ˙¿ ¶¨ ˛“
1940MPa , K
IC
· ‰ 141MPa m
[16 ,17]
¡£
2 ¡¡ ´ ˚ˇ ˚– —§†»—‚ —˝‚ ”¯ º —˜
– 1¡¢– 2 • – `—‡ `¸ —˝´ ˚ˇ ˚– —§†»—‚ ˜
»fl§ ‡ • ”˝ `ƒ § —˜
[14 ,18·35]
¡£
– 1 ¡¡ „œ˝ —˝´ ˚ˇ ˚– —§†»—‚ ˜ »fl§ ‡ • ( wt %)
Table 1 ¡¡ Chemical composition of overseas
typical maraging stainless steels( wt %)
Steel designation C Cr Ni Mo Co Ti Al Else element
PH13·8Mo ¡ 005 122Π132 75Π85 20Π25 ¡“ ¡“ 12 0005N
Custom450 0035 149 65 08 ¡“ ¡“ ¡“ 15Cu , 075Nb
Custom455 ¡ 005 110Π125 75Π95 ¡“ ¡“ 08 ¡“ 225Cu , 03Nb
Custom465 ¡ 002 110Π125 11Π112 075Π12 ¡“ 15 ¡“ ¡“
Pyromet X·23 ¡ 002 95Π105 65Π75 50Π60 95Π110 ¡“ ¡“ ¡“
Pyromet X·15 ¡ 003 150 ¡“ 29 200 ¡“ ¡“ ¡“
Custom475 ¡ 003 90 60 60 140 ¡“ ¡“ ¡“
D70 ¡ 003 115Π125 40Π50 40Π50 120Π140 ¡“ ¡“ ¡“
03Kh11N10M2T 003 1045 977 224 ¡“ 13 ¡“ ¡“
VNS25 ¡ 003 115Π125 90Π105 05Π08 ¡“ ¡“ ¡“ ¡“
VNS65 ¡ 002 134Π136 22Π26 39Π40 161Π163 ¡“ ¡“ ¡“
VNS59 ¡ 003 95Π105 88Π98 32Π36 65Π75 ¡“ ¡“ ¡“
Almar362 ¡ 003 145 65 ¡“ ¡“ 08 ¡“ ¡“
AM367 0025 140 35 20 155 04 ¡“ ¡“
000KH14N4K14M3T 002 145 40 29 146 026 ¡“ ¡“
03Kh11N10M2T2 003 105 97 20 ¡“ ¡“ ¡“ ¡“
03Kh12N8K5M3TYu 0028 115 78 23 53 095 033 ¡“
0Kh12N8MTYu 003 122 78 088 ¡“ ¡“ 08 ¡“
11Cr9Ni2MoTi 0015 110 90 20 ¡“ 15 ¡“ B < 0005
FerriumS53 021 10 55 20 140 ¡“ ¡“ 10W,03V
¡¡ ¡¡ – 1¡¢– 2 ¿ ¿· ‡ ,´ ˚ˇ ˚– —§†»—‚ ‡‹
˝ … Fe·Cr ( ¡ 12 %) ˛“ »ø ,˛“ `¸ Æ‚ ˘ ˙¿ ¨˝ —¡¢˜˝ ˚·
—, …¨º Mo ”˝ Al ¡¢Ti ¡¢Cu ¨ “ ¸ ,˝¤ „ ˚– —§ ı
´ ˚ˇ »ø ˛ ‡ · `¿ ˜ ˇ‚ —¡¡¢‚ ¶¨ ˆ ¢ • †…˜ ˙¿ »fl
ˇ ,»æˆ ‚ ˙¿ ¶¨ ¡¢‚ ¨˝ —, ‚ˆ ‚ —`…”ˆ ˜ ¿ ”‚ ‰
—,‚ ˜ ˙ ˙¿ –¨ ,—‰ˇ‚ ˜ ¶ˇ ` ¨˝ —¡£
– 2 ¡¡ —˝´ ˚ˇ ˚– —§†»—‚ ˜ `ƒ § —˜
Table 2 ¡¡Mechanical properties of typical maraging stainless steels
Steel designation
R
m
ΠMPa
R
p02
/ MPa
A % Z %
ƒ`/
(JΠcm
2
)
K
IC
/
(MPa¡⁄m
1Π2
)
Pyromet X·15 1550 1350 17 ¡“ ¡“ ¡“
Custom455 1724 1689 10 45 12J (V) 48
Custom465 1779 1703 14 51 ¡“ 71
Custom475 1979 1827 6 ¡“ ¡“ ¡“
Pyromet X·23 1779 1634 15 58 ¡“ 96¡« 104
0Kh16AN4B 1490 1140 16 67 ¡“ ¡“
PH13·8Mo 1620 1600 98 507 68 ¡“
VNS65 1800 1600 12 ¡“ 125 ¡“
VNS49 1200 1170 14 68 180 ¡“
VNS59 1400 1300 13 67 180 ¡“
D70 1656 1617 95 ¡“ 17 ¡“
000KH14N4K14M3T 1620 1470 20 62 76 ¡“
03Kh11N10M2T2 1720 ¡“ ¡“ ¡“ ¡ 14 ¡“
03Kh12N8K5M3TYu 1780 1620 ¡“ 55 ¡“ ¡“
0Kh12N8MTYu 2097 1568 73 265 ¡“ ¡“
3 ¡¡ ”ˇ ‰“ ¸ ˜ ˇ …‡ • Ł …˘
´ ˚ˇ ˚–—§ †»— ‚ —˜ ”ˇ‰ “ ¸ · ˘ ˆ “
—¨ ,» ˚˙ ˚„ ‚ —†»——”˝ ˜˝ ‚fl ˚· —˜ ˜ “
¸ ,¨ Cr ;» ˚˙ —˛‡ ‰˚ …˙¿ »flˇ ˜ ˙¿ »fl“ ¸ , ¨
Ni ,Mo ,Cu ,Ti ,Al ¨ ; ` » ˚˙ ˘‰” Ø fl –£⁄ ‚ —
¡ `¿ ˜ †— ´ ˚ˇ » ƒ˜·V9∑÷X5Ò9,¨ Ni ,Mn ,
Co ¨ , ˆ » Æ ˜ ˚˙ ‰—'˜Œ· ¶ ‚ˆ ‚ ”ˇ ‰Ł …˘˚–
‡£…¨º `¿ ˜ V ,B ,Nb ¨ “ ¸ ,¸ ˆ˙ ˘ ‰`¸ ˇ‚ »fl§ `£
‡ · ¡¢» »fl§ ‰˜ ˆ ¡£
31 ¡¡ ”ˇ ‰“ ¸ ˜ ˆ
‚ı ˚˙ ˚„ ‚ ¶ »fl†¢‚‡ Ł ˘ `…”ˆ ˜˝ ˚· —”˝ †»——˜
“ ¸ ,‚ ˜ ˜˝ ˚· —· nΠ8 „ ´ ‰ł˚‰˜ ˝» – ,¸ ¯
‚ı ”‹ `¿ ˜ Æ‚ ˘ †»——¡¢¿„ ı »fl˜ `ƒ ˆ ˇ Æ ‚ ,‚ı ¿
Æ‚ ‚ ˜ ·ª ˝‚ —,˚„ C ˙œˇ ˆ ˇ ˇ ˘ ,· ¶ł ‰˝
`¸ ·ª » ˜ ` ‰ ¨· ¸ ¶¨ ,˚„ ‚ ˜ ·ª ˝‚ —Æ ‚ ,†¢ ˚
˛´ ˝ ¿ ˆ ‰´ ˚ˇ Ø fl ,‚ı º ¯ ”ˇ ˜ Æ‚ ‚ ˜ ˜˝
”£¸fi‚fl˚· —,‰˝ ‚ ¶ ª ˚· ˜ ˆ ‚——
[15 ,36]
¡£ ´ ˚ˇ
˚– —§ †» — ‚ — Cr ”‹ `¿ … 12 % ,†»˝ 10 %¡£Cr ˚˙ œ
¸ —˛‡ “ ¸ ”˝ ¸ı —¡´ ˚ˇ ˙ł “ ¸ ,Cr ”‹ `¿ „ ‚ ,„
¨ ·ƒ ” ‚ —»Æ— `¿ ˜ œ ¸ Ø fl ,¶ł œ ¸ ˜ ·
»Æ ˇ ‚ ˜ ¨¨ ¸ —,‰˝ ‚ ˜ ˙¿ ¶¨ †¢¶æ»fl‚ ˜ ”Æˇ
2 †˜ ¡¡ `ˇ ¡¡ ¨¨ ¡¡ ·ƒ ¡¡ ¡¡ § ¡¡ –¤ 29
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
Menu
,Cr † ˚˙ ‰˝ M
s
ª ˜ “ ¸ fi »
[5 ,15 ,37 ,38]
¡£
˜ł ˚˙ ´ ˚ˇ ˚– —§ †» — ‚ — ˜ “ “ ¸ ,¸ ¿ Æ
‚ †»—‚ ˜ ˛» ”˝ ¶ »fl˙ª ˇ ,»„¿ ‚˜ ˘ ´ ˚ˇ †»—
‚ ˜ ˜˝ ˘ł ˚· ”˝ ˜˝ ˝` ¨ ‚fl ˚· —¡£Ni ˜ ”‹ `¿ †»˜ « ‚ ,
– · 10 %” ˜ł ‰«' · ƒˆ ˇ ˙ł ”˝ ‰˝ ´ ˚ˇ “ – ˛´
¶¨ M
s
,1 %˜ Ni ˝ ¿ ˚„ ˘ ‰˝ 50 ¡ ,˚„ ‚ ¥ ˚§ ·ª » ˜
`ƒ ,…´ ˚ ˛´ Ø fl —˜ †—` ´ ˚ˇ „ ¶ ,˚„ ‚ ˜ ˙¿ ¶¨
‰˝
[5 ,15]
¡£ ˜ł ¿ Æ ‚ ‚ ˜ ¸ — ”˝ ¨˝ — , – ˚˙ ‡‹ ˝
˛´ ˇ´ ˜ ¨˝ —, º ¸ ‰˝ ˛» · º …ˇ¶ › ˜ ‰»»¥ ˆ
˜ `¿ ˜ —˚ —„
[39]
,Ni »„ »Æ—˛‡ ˙¿ »fl ˆ ˜ ‰˚ …
ˇ , – ˚˙ —˛‡ ƒ˙·Ni3
Ti
[40]
¡¢ ƒ´ ·NiAl ˇ
[41 ,42]
¡£
“ ˚˙ … » » ˛¨ ¶¤ — ”˝ ¶ ·˛ † »fl —§ ƒ ,Æ ‚
‚ ˜ ˙¿ ¶¨ …` ˛˘ ¿„ `ƒ ,Mo ‚˜ ˘ » » ˛¨ ¶¤—˜ »œ ˚˙
˜ …¨º —˛‡ `¸ ˇ‚ —¡˜ ˆ ¯¯ `¢ •‰M
2
X ˇ , …`¸ ¶
·˛ † »fl—§ƒ
[43]
¡£ 2 % ˜ ¿ ˚„ ‚ †»˝‹ „ ¨ ·ƒ
ı …ˇ´ › ·ƒ ø –£‡ ‰ˇ‚ ˜ † ¶¨ ,« …‰»
¶¤ ( > 5 %) ” ,ƒ˜·V9∑÷X©I5÷…4, † ¶¨ ¿“ ˚…ˇ´

[44]
¡£ ˚– —§ ‡ı ˘ ˛ ‡ ˜ ‚» ˛ ‡ ˇ , ˙¿ »fl˜ ˝‹
˚– ˚„ ‚ –£‡ `…”ˆ ˜ ¨˝ —
[45 ,46]
,Mo ”‹ `¿ ˇ ¶ Fe ¶ł
,˚˙ » – ˆ » —“ ¸ ,‰«Ti » Cu · ‰ˆ ˙ł ˆ
»»‡ · , ·¸ ‰˝ `¸ „ ˚£ ˇ § ‰˛ ‡ ˜ ¿ ˜ —¡£
Æ‚ †»—‚ ˜˝ ”£¸fi ‚fl ˚· —˜ ,—˚ `ˇ – ˆ
[15]
,– †»—
‚ —˜ Mo ¡ 25 %˚– ,…·˚„ Cr > 25 % ,†»—‚ ”£ ¸fi
—˜ ˜˝ ˚· —† †» Æ‚ ¡£
˜ …¨º †¢†»—˛‡ ‰˚ …»fl”ˇ ˛ , Co ¶ »ø ˜
˙¿ »fl ˆ “ ˚˙ ‰˝ »ø ˜ ¶ ¶ †ª · ˜ ( stacking·
fault energy ,¸ı —·˛“ SFE)
[47]
, »„ ¿ ˘ ´ ˚ˇ —
˛» · ˙ ‰Æ„„ ˜ » ‚· ,˛“ ¸ ” ˜ ˛ ‡ ˇ —˛‡ Æ„' ‚ ¶ ˜
—˛”¸ ˛» ˆ ;—¿ – ˆ
[48]
,Co —‰˝ Mo ƒ`·Fe
[49 ,50]

˜ ¨ ‰ ¶¨ ¶ł … ‰ ˇ ˙¿ »fl ; Co »Æ· · ‰˝ ƒ˜·V9∑
¯
ƒ√
h◊5C8· √÷√1´C5C÷XI÷XM15,Co »„ ¿ Æ ‚ C ˜
» ¶¨ ,· ‰ł…»fl˛ ˜ ˛ ‡ ; Co ˚˙ ”ˇ ‰—˛¤ » ˜ Æ ‚
M
s
˛´ ¶¨ » ¶ M
s
ª ‰ ˝ ‰ˇ —¡ ˜ “ ¸ ,Co ¿ ——§
¿ M
s
˛´ ¶¨ ,« ˚˙ – Co ”‹ `¿ « ‚ »Æ· ‰ł´ˇ § ˜
—˛‡ , ¶ ‚ ˜ ¨˝ —†»ß ¡£¶ 12 %Cr ´ ˚ˇ ‚ ˜
—¿ ‰Æ„ß– ˆ , …`¸ ´ ˚ˇ – ˜ † ¶¨ , “ ˚˙
„ ¨ ˙¿ »fl˜ —§„ß ¡£
´` ˚˙ œ ¸ —˛‡ “ ¸ ,´` ´ ˚ˇ ˚– —§†»—‚ —
˜ “ ˆ ˘ ˚– —§˙¿ »fl˜ ˆ ¡£
˝› ˚˙ » ´ ˚ˇ —˛‡ “ ¸ ,˘ ˜ `ƒ ¶ ˝ ˜ł ,…
˚˙ ˜ł ˜ 30 % , Cu Æ ‚ ‚ ˜ ˜˝ ”£¸fi ‚fl ˚· —, ˛“ ˝› º
—¶ ¶ł …ı ”£œ ˛ ‚‰¯ ‡ ˜ ¨– ı ,· ¶ł Æ‚ `¸ ‚
˜ ˜˝ ¿ ˚· —,« ˝› ˜ …¨º ‰«˚„ ¨¨ …„⁄ —˜ – ˆ § ˜ ¡£
˝› ´ ˚ˇ ˚– —§†»—‚ — , ‚» ˝› ƒ¯ ˇ ˚„ ‚ ˙¿ »fl ,†¢
˙ Cu ˜ ˘ ‰„ ¨ ˙¿ »fl˜ ˆ ¡£
¶ ´ ˚ˇ ˚– —§†»—‚ ˜ ˇ ¸˘ ´` ,Ti ´
˚ˇ ˚– —§†»—‚ —˚˙ ——§˜ ˙¿ »fl“ ¸ ,Ti ˛“ ˙¿ »fl
“ ¸ …¨º Ni > 3 %˜ ‚ — , ˚– —§˚– —˛‡ ‰˚ …ˇ ƒ˙·
Ni
3
Ti ¡£Ti < 04 %˚– ˜‡ ‡ ¶¨ ˇ ¿ Æ ‚ ´ ˚ˇ “
– ˛´ ¶¨
[51]
, ˜ ”‹ `¿ „ ‚ ‰«…´ ‚ ˜ ` ˛˘ ˆ ‚——
…,Æ‚ ‚ ˜ · —˘˘ ¶ˇ ˙ª ˇ
[52]
¡£
Mn ˚˙ ' · ƒˆ ˙ł ˜ “ ¸ , ‚ — Mn ˛¨ ¶¤ ´ ˚ˇ
Ø fl ˜ ˜ `ƒ ‰·˛ Ni , ˚˙ ˙¿ ` Æ ‚ ‚ ˜ ·ª ˝‚ —“
¸
[53]
, ´ ˚ˇ ˚– —§†»—‚ — Mn ¿ ·œ Ni ,« Mn
˜ …¨º »Æ‰˝ Cr ”‹ `¿ ‰ˇ˝ ˜ †»—‚ ˜ ˜˝ ˚· —¡£
32 ¡¡ ´ ˚ˇ ˚– —§†»—‚ ˜ ‡ • Ł …˘
´ ˚ˇ ˚– —§†»—‚ ˜ Ł …˘˚– “ –£⁄ ‚ ˜ ˙¿ ¨˝
—¡¢˜˝ ‚fl ˚· —¡¢ ˜ ƒ˜·Fe ”‹ `¿ ”˝ ˚˚ `¿ ˜ †— ´ ˚ˇ
, ‡ • Ł …˘˚– “ ˙ : C ¡ 003 % ,˚„ ‚ ˜ »ø Ø fl
˛“ ı ´ ˚ˇ ,¸ ¿ ˚„ ‚ ˜ ˙¿ ¨˝ ——”ˆ ˜ ¯ ”ˇ ,
– ˚˙ ˚„ ˘ —”ˆ ˜ ¨˝ —,»„ ¿ ‚˜ ‰ł˜˝ ˚· —¡¢¿ ”‚ —
… ¨¨ …„⁄ —; ‚ı ”‹ `¿ ”ˆ · 12 % , ¡ `¿ †»˝
10 % , –£⁄ ‚ —ª „»˜ †»——º ˜˝ ˚· —; ‚ “ —
” ‚ ‰» ¶¨ ,˘ —˜ ˚ S¡¢P¡¢Si ¡¢Mn¡¢H¡¢O ”‹ `¿ “ ¡
`¿ ˝ , Æ‚ ‚ ˜ ˜˝ ˚· —¡¢¨˝ ¸ —”˝ ¿ ”‚ —, – ˚˙ Æ
‚ ˘£ ˝ —˜ ;ª „»”‹ `¿ ˜ ´ ˚ˇ ˛¨ ¶¤»fl“ ¸ (¨ Ni) ,
…¨“ – ˆ —˛‡ ƒ˜·V9∑, “ ˚„ ˘ †»†œœ „ `¿ ˜ †—`
´ ˚ˇ ;˚˚ – ”‹ `¿ ˜ ˚– —§˙¿ »fl“ ¸ , ¨ Ni ¡¢Mo ¡¢Al ¡¢
Ti ¡¢Cu ¨ , –ª —˛‡ ‰˚ …»fl”ˇ ˛ ¶ł ˚„ ‚ ˙¿ »fl ; ˛“ –£
⁄ ˆ ‰˚ ˛´ ˜ Ø fl ˚˙ ı ´ ˚ˇ ,‡ `¸ ¿ ˘ …”‹ `¿ ,
»„“ ¿ ˘ M
s
150 ¡ ,†¢« ¨• ¿ ˘ ˜ł – `¿ º ‚ı
– `¿ ˜ ¯ ”ˇ …˘ ¸ß ”ˇ ‰“ ¸ ˇ ¨ ¡£
¨¸ ˆ˙ Ł …˘» —´‚ ˚– ‡£˝¤ „ » —'› Ø „«˚‰
”˝ ˇ ˝…· ‡ı †‰¯—¶¤ ‚ˆ Ł …˘‡ • ˚˙ •æ”ˇ , Schaeffler
˝…
[54]
–» „ª •” ˆ ¯— ¶¤ »fl § ‡ • ¶ †» — ‚ ˜ —˝ ”˝
Ø fl ‰Æ„„ ˇ ˜ ‡ı †‰ ¡£ « ‚ˆ ˝… · ¯ ” ¶ ¨– ˇ ,
¨ ”ˇ ‰“ ¸ Co ¡¢Cu¡¢Ti ¡¢Al ¨ ¶ Ø fl ˜ ˇ ˆ» —¿…´˙ ,
´ ˚ˇ —˝”˝ ´ ˚ˇ —˝‚ ƒ˜·V9∑h◊$=•√-¯hC4ƒ¨$
$VhC÷R,Potak ”˝ Sagalevich
[55]
‚ø 110 ‡ • †»˝‹ ˜
†»—‚ …· `¿ ˛˜ ˇ ˚ ,…˘¸ª †¢» ‡ `¸ ”ˇ ‰“ ¸ ˇ ¶
Cr ¶ œ ¸ ”˝ ´ ˚ˇ —˛‡ `¿ ˜ ˇ ˚ ˝…(¨ ˝…
1) ¡£˝¤ „ ¶ Ł …˘˜ ”ˇ ‰‡ • ¶ ƒ ˜ “ ¸ ¸ø …˘¸ª ˆ
‰– `¿ ,¶ ‚ˆ ˝…” ¿ ‡ı †‰¯—¶¤‚ˆ ”ˇ ‰‡ • ˜ ˚ ˛´
Ø fl , · · …ı `¸ ¿˘ —„⁄ `¿ ¡£¨ ˝…1 ¸ø ˚ , X
Æ – ˚ ¸ø — ”ˇ ‰“ ¸ ˇ ¶ Cr ¶ œ ¸ —˛‡ `¿ ˜
3 4 ˘ ´ ¨ :´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
Menu
,…· Cr
F
equ
(„« ˚‰1) ; Y Æ – ˚ ¸ø — ”ˇ ‰“ ¸ ˇ ¶
Cr ¶ ´ ˚ˇ —˛‡ `¿ ˜ ˇ ,…· Cr
M
eqv
(„«˚‰2) ¡£
˝…1 ¡¡ ‚ı – `¿ ¶ †»—‚ ˚ ˛´ Ø fl ˜ ˇ
[55]
Fig. 1¡¡Effect of Cr
F
eqv
and Cr
M
eqv
on microstructure of stainless steel
[55]
Cr
F
eqv
= %Cr·15 ¡` %Ni + 2 ¡` %Si·075 ¡` %Mn·K
F
¡`
( %C + %N) + %Mo + 4 ¡` %Al + 4 ¡` %Ti + 15
¡` %V + 05 ¡` %W + 09 ¡` %Nb·06 ¡` %Co·
05 ¡` %Cu (1)
Cr
M
eqv
= 20[ %Cr + 15 ¡` %Ni + 07 ¡` %Si + 075 ¡` %Mn
+ K
M
¡` ( %C + %N) + 06 ¡` %Mo + 15 ¡` %V
+ 11 ¡` %W + 02 ¡` %Co + 02 ¡` %Cu + 19
¡` %Ti·01 ¡` %Al ] (2)
4 ¡¡ ´ ˚ˇ ˚– —§†»—‚ ˜ ˙¿ ¨˝ »fl»œ
41 ¡¡ ˙¿ »fl»œ
411 ¡¡ ı ´ ˚ˇ ˇ – ˙¿ »fl
´ ˚ˇ ˚– —§†»—‚ › „ ¨ ·ƒ ” »ø Ø fl ˛“ ‚
ˆ ¶¨ ˛» · ˜ ı ´ ˚ˇ Ø fl ,ˇ ` ˜ ´ ˚ˇ ı ˛» ˇ
ˇ ˝‹ ,ˇ »¥fi … —¡˙ª ‰˙§ ‰‰·¥ , ı ˜ ¿ ¶¨ ˛“
002¡« 31ƒm ,§ `£ · —¡¶ ı ˜ ¿ ¶¨ ”˝ • †…ˆ» —
ˇ ;˙ ‰Æ„„ “ ˚˙ ˛» · ¡¢…« `¿ ˜ ´ˇ § ,˛» · ˆ ¶¨ ¿ ·
10
11
¡« 10
12
cm
- 2
; —˜`¢ •‰‰Æ„„ ˜ ´ ˚ˇ ¿ – ˛´ »
¨ ˛´ „ ‡ ——˛‡ ,´ ˚ˇ ˜ ˙ • ˙¿ ¶¨ …˛“ 686MPa ,
—`…”ˆ ˜ ¸ —”˝ ¨˝ —¡£
412 ¡¡ „ ¨ ˙¿ »fl
”ˇ ‰“ ¸ ˆ »»» …ˇ¶ ˜ —˛˚‰¨ ¨º »ø ‰˚ ˜
§ ‚æ— , › ‡ · —§ƒ ¡¢fl —˜£ `¿ —§ƒ ”˝ „ ¨ —
—»fl˜ ˆ ¶ł ˚„ ‚ ˙¿ »fl ,˘ ˙¿ »fl—§ƒ ¸ ¯ “ ¸ ”‹ `¿
…¶ł ˆ ˇ ,¨ ,¨ …`› º ¨ ˚ › ˜ ‡ · † , ‡
˜ „ ¨ ª »ß– ,—˛‡ ¨ ˚ › ˛“ ——˜˜ fl —ƒ
– ‡¡ ,Ł › ˛» · ¸ ¶fl¶ł ˙¿ »fl ,› · —¡† – œ · ˙¿ »fl
—§ƒ † œ · ;„ ¨ ˙¿ »fl˜ ‡ ¶¨ ,† ¨¡ »ø Ø fl ,…
ˇ¶ “ ¸ C¡¢N ¶ ´ ˚ˇ Ø fl ˙¿ »fl—§„ß · ¡£
413 ¡¡ ˛ ‡ ˙¿ »fl
´ ˚ˇ ˚– —§†»—‚ › ˚– —§·ƒ ı ´ ˚ˇ »ø
ˇ ˛ ‡ · `¿ ˇ‚ —¡¡¢ˆ ¢ • †…˜ ‰˚ …»fl”ˇ ˛ ˚˙ ˚„ ‚
»æˆ ‡‹ ‚ ˙¿ ¶¨ ˜ „ …¡£ ´ ˚ˇ ˚– —§†»—‚ —‡£…ß
˜ ˛ ‡ ˇ —† ˙ · Fe
2
Mo —˝Laves ˇ ¡¢R ˇ ,ˇ‚ ‡⁄ ·
˜ ƒ˙·Ni3
T¡¢Ni
3
Mo ,†»„ —˛·
ƒ
ˇ ¨ ¡£– 3 ˛“ ´ ˚ˇ
˚– —§†»—‚ ‚ —‡£…ߘ ˛ ‡ ˇ
[15 ,18 ,34 ,41 ,56 ,57]
¡£
– 3 ¡¡ ´ ˚ˇ ˚– —§†»—‚ ˜ ˛ ‡ ˇ
Table 3 ¡¡ Precipitate phases in maraging stainless steel
Steel designation
Aging
temperatureΠ
Precipitate
PH13·8Mo 450¡« 500 NiTi ,NiAl
AM367 427¡« 510
ƒ
·Phase , Laves·Phase ,
Mo·Compounds , Ti·Compounds
Ultrofort401 500¡« 550
ƒ
·Phase ,Fe
2
Mo ,Ni
3
Ti
1RK91 475¡« 550
Ni
3
( Ti ,Al) ,R·Phase ,
Laves·Phase , R¡fl·Phase
00Cr12Ni5Mo5Co5Ti05 500¡« 700
ƒ
·Phase ,Ni
3
Ti ,R·Phase
00Cr12Co12Mo5Ni45¡« 60 500¡« 525 R·Phase , ƒ·Phase
03Kh11N10M2T 500¡« 550 Ni
3
Ti
03Kh11N10T 600¡« 650 Ni
3
Ti ,Fe
2
Ti
42 ¡¡ ¨˝ »fl»œ
421 ¡¡ †—` ´ ˚ˇ ˜ ¨˝ »fl
†—` ´ ˚ˇ ı ´ ˚ˇ ˚ł fi …» ˘‹ · ´ ˚ˇ
˛§ ‡˚ –¡ ˘‹ · • †…,¶ ‚˜ ˘ †˜ `ˇ ˜ ¨˝ —˚fi • —ß ,†»
‰¿ Ł „ ` ˛˘ ´ ˚ˇ ı …˜ ' „ ,»„¿ …ı»”
ı …ˆ …fl¯¯ `—˚– ˛» · ˙ ¶¸ ˘ ˜ ƒ `ƒ …fl— , Thomas
[58]
ł — ¿ „ Fe·Cr·C ˇ ´ ˚ˇ ‚ ,† „ † ‰`¸ ¶ˇ ` ¨˝ —
º †—` ´ ˚ˇ ˜⁄ —„ ,¨ˇ ˛“ ˛¨ ¶¤˜ †—` ´ ˚ˇ –¡ ˜⁄ ·
ı ´ ˚ˇ fi …¶ ¨˝ ——ß ¡£
422 ¡¡ —˛– ¨¨ ·ƒ Æ‚ ¨˝ —
—˛– ¨¨ ·ƒ ¿ ——§‚˜ – ´ ˚ˇ ˚– —§†»—‚ ˜ Ø
fl ,ˇ‚ »fl‚ ˜ ¡ ——§§ `£ ‡ · ¡–,¸Ø»fl ı ´ ˚ˇ ,Æ ‚
˛» · ˆ ¶¨ †¢‚˜ – ˛» · Ø ‹ ,¶ ˚– —§˙¿ »flˇ ˜ ˛ ‡ ‚ ˛“
—ß , Æ‚ ˙¿ ¶¨ ˜ ˝‹ ˚– ‚˜ ˘ ‚ ˜ ¨˝ —¡£
4 †˜ ¡¡ `ˇ ¡¡ ¨¨ ¡¡ ·ƒ ¡¡ ¡¡ § ¡¡ –¤ 29
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
Menu
5 ¡¡ ´ ˚ˇ ˚– —§†»—‚ ˜ ‰ł„
˜¿˙ ,´ ˚ˇ ˚– —§†»—‚ ˜ œ †œ† ˆ `¸ « `ˇ ¡¢‡‹
‚ ‰» ¶¨ ¡¢‡‹ ‚ ø ¨ »fl …¨« ` ‡ ˜ ˇ‚ Ø fl ¿ ˘ ¨ ˇ¨
‰ł˜ œ †œ„⁄ ……˚ı , ˚„ ˆ ‚ˆ ‚ ˜ —˜ —`¸ ‰ˇ· ˜ Æ
‚ ,†¢ ” ‚ ˙¿ ¶¨ ¡¢¨˝ —¡¢†»—˜˝ ˚· —”˝ › …ˆ¿ ——˜ …
„⁄ ˘ —˜ ˜ ˝Œˆ ¯ ”ˇ ¶ł ‚ ¸ ‡ ˛“ ‚ ¿˘ ……` „ …
Ł –‚ ˜ ‡—`ƒ ˜˝ ˚· (» ‚ ˛´ ) †¿…˜ ˚ ¡ †˜ `ˇ ¡£
‰…‚˜Œ,‚ œ —¿ ” ”˝ ¶«–– ˚ ‚ „«¸ † ˆ 3t
¿ ‚—ƒ ´fl + ¿ ”˜ ´fl – `¶ »æˆ » —´—˝˜
ƒ 200mm( †˜ ) ¡¢R
m
¡ 1900MPa ¡¢K
IC
· ‰ 141MPa m
˜ ˜˝ ”£ »• ‡ ‚fl˚· ˜ ´ ˚ˇ ˚– —§†»—‚ ,‚ˆ ‚ ˚˙ ˛ „œ
—˘ —„œ…˚ˇ¨ ‰ł¸fi ˘‰˜ ‚ ¨˝ —‡‹ ‚ ˙¿ ¶¨ †»—
‚ ,˘ ”‰¿ ”‰ ……˚ı ¡¢”£ ……˚ı ¡¢ˇ¨ ‰ł˜ · ……˚ı ¨ •‰
ˆ † —˙– ˜ ˆ ˝ ¡£ º ·¸ ˝‹ ˚– , »„ ¿“ •¢ `¸ R
P02
¡
1200MPa ˜˝ ”£¸fi‚fl˚· ´ ˚ˇ ˚– —§†»—‚ ,‚ˆ ‚ —`…
”ˆ ˜ ˜˝ ”£¸fi»• ‡ ‚fl˚· —…`…”ˆ ˜ „⁄ —˜ ¨ ¡£
PH13·8Mo ˚˙ » —‚ ˙¿ ¶¨ ¡¢‚ † ¶¨ …¯ `…
˜ ¿„ ‚fl˚· —˜ ˜ ´ ˚ˇ ˚– —§†»—‚ ,¸ø —‡` † »fl†»
—‚ —˙¿ ¨˝ —¯ ”ˇ ”ˆ ˜ ,¿ ˆ ”‰ ¡¢”¸ •· ƒ ¶
…˚fl˝ »fl„⁄ ¨ —— ; PH13·8Mo ˚˙ ‚ …¶ ”‰¯ ˚
†˜ `ˇ , “ ˆ ˘ ¸˜ ·œ• »œ¡¢‰¢ • »œ—˛´ ˜˝ ˚·
˜ “ ‡—`ƒ „„ …, …˘ ”‰ ¡¢”‰¿ • »œ¡¢» …•¢ ¶fl
»œ¿ …¡¢•¢ ‰Æ„„ …,†¢ ˇ —• »œ»œ A380 ¿˝ »œˇ
˚„ ˆ
[59·61]
¡£ Martin ¨ ¨¸ • – 1997 ˜Œ”˝ 2003 ˜Œ»æˆ
`¸ Custom465
[10]
”˝ Custom475
[11]
˜ •¢ ˆ ¤ ß , ˘ —
Custom465 ‚ “ ƒ ˆ …fl ¿˙ ¨ „ …Ł –‚ ˜ ‡—
`ƒ ˜˝ ˚· (» —˛´ ) †¿…˜ ˚ ¡ †˜ `ˇ ¡£
‰˜Œ· „œ˝ ¿“ •¢ ˜ HSL180 ‚ ˚˙ Cr·Mo·Co·Fe ˇ
˜ ´ ˚ˇ †»—‚ ,˘ ”‹ —‰ˇ‚ ˜ Co ”˝ … Mo ˚ ˝…
ˆ ‰‚ ˙¿ ¶¨ ”˝ ‚ ¨˝ —,º 4340 ‚ ¨ ˝ ”ˇ ‰‚ ˜ —
ˇ ˝‹ ˜ ¿„ › ˙¿ ¶¨ (· …˛“ 1800MPa) ,HSL180 –»`—˛“
AMS5933 –Œ…
[61]
¡£
ˆ „œ QuesTek —´……˚ı —ˇ ¨˛ „«¸ 2002 ˜Œ¸
ˆ …˘¸ª »œ……˚ı Ł …˘» —´—˝˜ ¶ ·˛ † »fl‡‹ ‚ ˙¿ ¶¨ ´
˚ˇ †»—‚ · ·œ ˇ • ˜ Aermet100 ‚ ,› œ `¸ 4
˜Œ¶ ˜ ˚– …‡ „ƒ—˘ ‡ FerriumS53 ,‚ˆ ‚ ˜ ˙¿ ¶¨ ¿ ·
1980MPa , K
IC
· ‰ 80MPa m
[14]
¡£
¡ ˚fi » ˛ ¡–˘ … „œ … · `ƒ § ‡ •¢ „ ‚ — ˜ ¡¢‚ ˘• ˚
˜ ‡‹ ‚ ˙¿ ¶¨ †» — ‚ ,‰ł» †‰˝˘ ¶fl`¸ ‚ˆ ‚ ˜ •¢ „ ,
¨ ,‚ ˙¿ †»—‚ ‰Æ„„ „ƒ˜ » »fl†˜ `ˇ ‚ ˙¿ ¶¨ …·¯ †»—
‚ ˜ ¿“ •¢ ,· „ ‚æ¶˝ …ƒ 400mm ‡‹ ‚ ˙¿ ¶¨ †»—‚ ˜ —
˘ ¨ ,¶…ˇ ˚ ‚ˆ ‚ ˜ •¢ „ —¶ •‰ˆ —`¸ ‚ „ª
•” ˜ ˆ ˝ ¡£
6 ¡¡ „ ˝ß
¸ ¯ ´ ˚ˇ ˚–—§ †»— ‚ ˜ ˙¿¶¨…¶ –… ”ˇ— ˜
˜ Æ‚ ,‚ˆ ‚ ”‰¿ ”‰ ¡¢”£ ¨ ` ˜ ƒ ˆ ˜ ˙
˚fi• „ª « ,˝ ˜¿ ˙ ‚ˆ ` ˜ •¢ „ · ¿ Ƈ …‚ª „ ˝ß :
1) ´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „ ‰«† ˆ « ¨• ¿ ˘ º
‡‹ ‚ ‰» ¶¨ ( [ H] + [O] + [N] + [ S] + [ P] ¡ 40 ¡` 10
- 6
(ppm) ) ˜ ¨ `¶ ……˚ı , ¨« ` ‡ ˇ‚ § ¿ ˘ …‡ • ø ¨
»fl¿ ˘ ……˚ı , · •ø Æ ‚ ˇ —‚ —˜ ˜ ˝‹ ˚– ,—˘
‚ ‚ ˙¿ ¶¨ ¡¢‚ ¨˝ ¡¢ ”ˇ —˜ ¯ `…˜ ´ ˚ˇ ˚– —§†»—‚ ;
2) ‚ —§”˝ › »• ß ˆ ˚ · ˛“ ”¸ —˜, ˚—‡¡ —Ł˙ ˛“
ˇ … , —´˜ · ……˚ı ¡¢”‰¿ ”‰ ”˝ ”£ ……˚ı ˛“ ‰´
ª ,•¢ „ ˚ · ‰˚¡ —˝¡¢»• –£—˝´ ˚ˇ ˚– —§†»—‚ ,
¨ , Mn ,N †¿• ·œ Ni ,ˆ Ti †¿• ·œ Co ,ˆ W ”˝ Ti
†¿• ·œ Mo …¶ “ ‚· ”ˇ ˛¢ ”ˇ ‰»fl…˝ ”ˇ ‰»fl¨ ;
3) •¢ „ — ˚ —˜ ˜ ´ ˚ˇ ˚– —§†»—‚ ,
¨ ,`…”ˆ …„⁄ —¡¢¿ ¸ —˜ ‚ , ‡‹ ˝ ˛´ º ˜˝ —˛´ ‚
,˜˝ ‰ˇ¿` ¿ ‰Ø˚ ‚fl ˚· º ˜˝ ˜¥ ˚· ‚ , …‚ ¿„ ˘£ ˝
—‚ ¨ ;
4) ‚ ˙¿ †»—‚ ‰Æ„„ „ƒ˜ » »fl†˜ `ˇ ˚˙ ‚ ˙¿ ¶¨ †»
—‚ •¢ „ ˜ “ ˙ ˚˘ fi » , ¨ ,‚ ˙¿ ¶¨ ˛ ·¯ †»—‚ ,
‡` † »fl¨ ·¯ †»—‚ ,˝ ¯ ˝ †»—‚ ,…ıæ †»—‚ ¨ ;
5) †»¶ˇ »fl‚ ˙¿ ¶¨ †»—‚ ˙¿ ¨˝ »fl»œ ´ ˜
»ø·¡ ˇ ,‰Łœ ˇ ·œ…˘¸ª »œ……˚ı º †˜ `ˇ ¿˘ § ‰Æ”ˇ ¶ł ‡ ˇ
˜ ¡ †˜ `ˇ ˛¢ „ ‰Æ„„ Ł …˘¡–—´—˝¿˘ —‡ „ß ,« ¨• Ł …˘,•·
‚· ˚ …ø, †‰˚ ˇ · ˘ ¶¤—˜ Ł …˘‚ ˙¿ ¶¨ †»—‚ ˜ ‰
´ ˜¿ –Œ¡£
´ —»:‚——»‚ œ —¿ ” ˇ¨ · ‰˚ ”˝ ¸˛ ˛“ ¸‡ ‰˚ ¶ – ˛˜ Æ
‡ ˜ –ƒ„ …ß¡£
†˛ ¿… ˛˜ ˇ
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7 4 ˘ ´ ¨ :´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „
© 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
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43 ¡¡ 3 ˘
¡¡ 2 0 0 8 ˜Œ 3 ´
‚ œ
Iron and Steel
¡¡ Vol. 43 , No. 3
March ¡¡ 2008
´ ˚ˇ ˚– —§ †» — ‚ ˚– —§ ˛ ‡ ˇ … ˛» ˇ „ ˇ ˜ — ¿
‡´ …˛
1
, ¡¡ `ı ¡¡ ‰›
2
, ¡¡ ¿ ‰
1
, ¡¡ ¯ ¨¤
1
(1. —„œ‚ —¿˘ ………fl˝¯ „«¸ ‰Æ„„ †˜ `ˇ —¿ ¸ø , ––' 100081 ; ¡¡ 2. —„œ‚ —¿˘ ………fl˝¯ „«¸ ¿˘ ……—¯ˇ¢ ˚ , ––' 100081)
“ ¡¡ “ : ˇ ˝‡ —¿ `¸ Custom 465 ‚ 510 ¡ ˚– —§˛ ‡ ˇ …ˇ „ ˜ ˛» ˇ „ ˇ ,‰Æ„ß– ˆ : Ni3 Ti ˚˙ ‚ ˜ “ ˚– —§˛ ‡
ˇ ,˛ ‡ ˇ ˛“ ‚¸ · ,‚¸ ˜ ‡⁄ ¶¨ •‰ˇ º ´ ˚ˇ »ø ˜ [ 111 ]M •‰ ˇ » ´ ; (011)
M/ / (0001)
Ni
3
Ti ¡¢[ 111 ]M/ / [ 1120 ]Ni
3
Ti ˚˙ ´
˚ˇ ”˝ Ni3 Ti ‰˚ …»fl”ˇ ˛ ¨• ˙—˜ ˛» ˇ „ ˇ , ˛» ˇ „ ˇ ˚„ Ni3 Ti ´ ˚ˇ »ø ˜ ‡ ˇ 12 ¿ ˜ ˜ ˙ —˝¡£
„ …·˚ : ˛ ‡ ˇ ; Ni3 Ti ; ˚– —§; ´ ˚ˇ ˚– —§†»—‚
—˝…• ”¯ : TG142. 7 ¡¡ ¡¡ ˛˜ ˇ –Œ˚¶ ´º : A ¡¡ ¡¡ ˛˜ ´ – ”¯ : 04492749X(2008) 0320081205
Research on Precipitates and Relationship With
Martensite of Maraging Stainless Steel
CHEN Jia2yan
1
, ¡¡L IU Jiang
2
, ¡¡ YAN G Zhuo2yue
1
, ¡¡ ZHAN G Yong2quan
1
(1. Instit ute of St ruct ure Materials , Steel Research Technology Group Corporation of China ,
Beijing 100081 , China ; ¡¡ 2. Depart ment of Science and Technology Information , Steel
Research Technology Group Corporation of China , Beijing 100081 , China)
Abstract : The aging precipitates and t he relationships wit h martensite of Custom 465 were researched. The result s
show t hat Ni3 Ti is t he major precipitate in t he steel. The precipitates take t he form of poles wit h t he longit udinal ax2
is parallel to [ 111 ]M . The relationships between t he precipitates and t he martensite are ( 011)
M/ / ( 0001)
Ni
3
Ti
[ 111 ]M/ / [ 1120 ]Ni
3
Ti . These relationships make Ni3 Ti precipitate in 12 kinds of possible variant s.
Key words : precipitates ; Ni3 Ti ; aging ; maraging stainless steel
… ‰Ø: ‡´ …˛ (19692) , ˜—, †' ˚¿ , ‚ …¶„⁄ ‡ ˚ƒ ; ¡¡ ¡¡ E2mail : chenjiayan @nercast . com ; ¡¡ ¡¡ —¶' ¨ ˘ : 2007207205
¡¡ ¡¡ ¸ø “ ,˝¤ „ ˚– —§˛ ‡ ¿ ˚„ Co ¡¢Mo ”˝ Ti
”ˇ ‰»fl˜ ˝ …´ ˚ˇ ‚ »æˆ ‡‹ ‚ ˜ ˙¿ ¶¨ , ˝‹ ˚–
–£‡ `…”ˆ ˜ ¨˝ —”˝ ¸ —¡£¨ 20 ˚ …˝60 ˜Œ·œ‡ı ¿“ •¢
˜ 18 %Ni ´ ˚ˇ ˚– —§‚ ,˝¤ „ ˚– —§ ¨˝ —˜ ´ ˚ˇ
»ø ˜ ˛ ‡ Ni3 Mo ¡¢Ni3 Ti ”˝ Fe2 Mo ¨ ‰˚ …»fl”ˇ
˛ , ¿ ˚„ ˙¿ ¶¨ · ‰2000 MPa ˇ ¡£˜¿ ˙
› ¿“ •¢ ”‹ Co ˜ C250 ¡¢C300 …¶”˝ ˛ Co ˜ T2250 ¡¢
T2300…¶´ ˚ˇ ˚– —§‚ »æˆ „ª •” ˜ ƒ ˆ , ¨ ˘ ˚˙
”‰ ¡¢”‰¿ ¡¢ ˚´ ”˝ ”¸ „⁄ ` ¡£« ·« ˝‡ ˜ 18 %
Ni ´ ˚ˇ ˚– —§‚ ˜ ¿„ ˚· —” † ,ˇ ˘ `¸ ‚ˆ —˝‚
˜‡ —'` ˜ ƒ ˆ ¡£` » •‰ˆ ,·« ˝‡ ‡` † »fl†»—‚
¸ ¨» —ª „»˜ ‚fl ˚· ¿„ `ƒ ,« “ ¿¿ Cu¡¢…»fl˛
» ——ˇ ˙¿ »fl , ·¸ ˙¿ ¶¨ ˛ •¤ º ·« ˝‡ ˜ ´ ˚ˇ ˚– —§
‚ ˇ –¨ ,¨ PH1328Mo ‡` † »fl†»—‚ ,˝¤ „ B2 ‰Æ
„„ƒ´2NiAl ——ˇ ”˝ M2 C …»fl˛ ˙¿ »fl
[ 1 ]
,˙¿ ¶¨ ‰˜
· ‰ 1 300 ¡« 1 600 MPa , ¶ł ¿¿ Cu ‡` ˛ ‡ ˜
PH1525¡¢Custom 455 ¨ ˜ ˙¿ ¶¨ ‚ ˝ ¡£¸ ¨» † —
… Ti ¡¢Nb ¨ ˙¿ »fl˜ †»—‚ , « ˙¿ ¶¨ ¨ ˘« ˝ ¡£ˆ „œ
Carpenter „«¸ ¿“ •¢ ˜ Custom 465 ´ ˚ˇ ˚– —§†»—
‚ ,510 ¡ ˚– —§ı …ˇ´ ¿„ › ˙¿ ¶¨ · ‰1724 MPa ,–¨ ·«
˝‡ ˜ PH †»—‚ ˙¿ ¶¨ ‚ ‡ 20 % ˇ ,†¢ —¯ `…˜ ¨–
¿ › ˙¿ ¶¨ ”˝ ¶ˇ ` ¨˝ —¡£„ ˚– —§ı …ˇ´ (540 ¡ ˚–
—§) ,º ·« ˝‡ ˜ PH †»—‚ (¨ Custom 455 ”˝ 1328 †»
—‚ ) ˇ –¨ ,¨ —¯ `…˜ ˙¿ ¶¨ ¡¢¨˝ —”˝ SCC ¿„ `ƒ Ø
”ˇ ¡£
Custom 465 ‚ ˜ »fl§ ‡ • º ·« ˝‡ ‚ ˙¿ †»—‚
· …«· ˜ † ,˘ ˙¿ »fl˛ ‡ ˇ …ˇ ƒ ˜ ˙¿ »fl»œ˘
– ¨» —‰ˇ· ˜ † , ·¸ —¿ ˚– —§˛ ‡ ˇ ˜ —˝¡¢ˇ
ƒ ˜ § ‰Æ„„ …º »ø ˜ ˛» ˇ ”˝ ˘¥ ¯ „ ˇ ,¶ ‰
¸ Custom 465 ‚ ˛ ‡ ˙¿ »fl»œ˘ ˚˙ ˚fi • “ ˜ ¡£˛“
·¸ –˚ ‰Łœ ˝‚ ˇ ˛¢ ( TEM) ¶ ¸« ¿ – `¶
˜ Custom 465 ‚ ˜ ˚– —§˛ ‡ ˇ ‰ł——`¸ • ˛ ,ˆ ‰`¸
˛ ‡ ˇ ˜ —¡¢§ § ¨ “ ‰Æ„ß ¡£
1 ¡¡ ˚ Ø †˜ `ˇ º ˚ Ø •‰•¤
ˆ 350 kg ¿ ‚—ƒ ´fl – `¶ ” ‰‰¢ ‡ 2 § …«
, …« › ¿ ”˜ ¨ ¡£‚ ¶§˜ »fl§ ‡ • (˚ `¿
• ˚ , %) ˛“ : C 0. 004 , Si 0. 026 , Mn 0. 013 , S
01004 4 , P 0. 004 , Cr 11. 72 , Ni 10. 83 , Mo 1. 05 ,
Ti 1. 68 , Al 0. 083¡£ ¨ ˜ ‚ ¶§› „ 1200 ¡ ¡` 8 h
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43
ø ˚ »fl·ƒ ” , ¶˝ ‡ 40 mm ¡` 90 mm ¡` 200 mm
˜ ¯ ¡£ ¯ › „ ¨¨ ,†¢› 980 ¡ ¡` 1 h „ ¨ ·ƒ
” ‡ 0. 3 mm ”˝ 1. 0 mm ”æ˜ †˜ , –
—˛`¿ • – ¿ ˘ … 30 %”˝ 70 %¡£ —´„ ¨ ”˝
˜ †˜ ˇ ˙—¨¡ 12 mm ¡` 16 mm ˜ –¡ ˘‹ ˚ ø ¡£‚ø
Ø“—¿ ˆ ‡ ˜ ¡ 510 ¡ ¡` 4 h ˚– —§” ”ˇ `ƒ § —
˜ …¡–˜ ‰Æ„ß
[ 2 ]
,†¢¿…´˙ ‰˝‚ “ ˙
˛ ‡ ˇ —ª „»˜ ˙¿ ¶¨ ,–˚ † ˆ 510 ¡ ¡` 24
h „ ˚– —§ –ª ˚„ ˛ ‡ ˛ ‡ • ‡⁄ · ¡£˚– —§” ˜ 12 mm
¡` 16 mm ˜ –¡ ˘‹ ˚ ø ˆ ˚ „⁄ …ı–¡ ` 0. 05 mm ” ,ˆ
‰¸« ¯ - 20 ¡ ˇ´ …ı–¡ , ‰” ˛“ 5 %˜ ‚ ´¨
¸Æ+ 95 % ·…¨ ” ,˘ ‡ ˜ –¡ ˜⁄ ø ˘• ˆ H2800 ˝‚
„ † ,† „ ˛“ 200 kV ¡£
2 ¡¡ ˚ Ø ‰Æ„ߺ • ˛
2. 1 ¡¡ ˚– —§˛ ‡ ˇ ˜ ¨• ¨ˇ
˝…1 ˚˙ —ˇ ˚ »fl§ ‡ • ˜ Custom 465 ‚ ›
980 ¡ ¡` 1 h „ ¨ ¡¢ – —˛70 % ,¸ ” 510 ¡ –£
˛´ 24 h ” ˆ ‰˜ TEM ˘‹ ¡£· ˝…1 (a) ˜ ˆ ‡¡ ˇæ
(BF) ¿ ¿· ‡ ´ ˚ˇ »ø ˜ · …«ˇ‚ —¡˜ ˆ ¢ ˛
‡ ˇ , ˚ł ¨º •‰ˇ ‰‰˘‰——´ ˚ˇ ˜ § ·ł
Æ [ 100 ]M ˚– ,¿ „ † ‰´ ı ˛˘ (˝…1 ( d) ) ,¸ ˆ ˛
‡ ˇ ˜ · ,˚˚ – ˙ª “ ˚ ø ” ˆ ‰¶ ‡˘ ˜ ˛ ‡ ˇ
»¤ø (˝…1 ( b) ) ,› • ˛ ¨• ¨ˇ ˛ ‡ ˇ ˛“ Ni3 Ti ¡£¸
” †»˝‹ ˝ ‚ ˚ ´ ˚ˇ § ·ł Ƙ † ⁄ ˚ ˛ ‡
ˇ ˛“ Ni3 Ti ¡£
2. 2 ¡¡ Ni3 Ti ˛ ‡ ˇ ˙ —˝…˘ º »ø ˜ ˛» ˇ „ ˇ
Ni3 Ti ‰˚ …»fl”ˇ ˛ ˚˙ Ti ˙¿ »fl˜ ˚– —§”ˇ ‰—
“ ˙¿ »fl˛ ‡ ˇ fi »
[ 3¡« 5 ]
, Fe2Ni2Mn2Ti ¡¢Fe2Cr2
Ni2W2Ti ”˝ Fe2Mo2Ti ( T2200 ¡¢T2250¡¢T2300) ‚ —ø
•¢ ˇ Ni3 Ti ‰˚ …»fl”ˇ ˛ ˚˙ “ ˚– —§˛ ‡ ˙¿ »flˇ ,
Ni3 Ti º ´ ˚ˇ »ø fi …˜ ˛» ˇ „ ˇ æ · ˆ ¯¯ ˆ /
ˆ ¯¯ ˆ ¡¢ˆ ¯¯ •‰ˇ fi …• – ˘‰——, …·: { 110}M/ /
{0001}Ni
3
Ti ¡¢ < 111 > M/ / < 1120 > Ni
3
Ti ¡£
(a) ˆ ‡¡ ˇæ ; ¡¡ (b) (a) ˜ ¡ ˙ł »¤ø ; ¡¡ (c) ˆ (2022)
Ni
3
Ti ˆ ‰ ˜ — —˜ ‡¡ ˇæ ; ¡¡ (d) (c) ˜ ¡ ˙ł »¤ø ; ¡¡ (e) »¤ø ‚ ˚ »fl
˝…1 ¡¡ › – —˛70 %¡¢510 ¡ –£˛´ 24 h ˚ ø ˜ TEM ˘‹
Fig. 1 ¡¡ Diagrams of the specimen cold rolled with 70 %reduction rate ,and aged at 510 ¡ for 24 h, TEM
¡⁄ 2 8 ¡⁄
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3 ˘ ‡´ …˛ ¨ :´ ˚ˇ ˚– —§†»—‚ ˚– —§˛ ‡ ˇ …˛» ˇ „ ˇ ˜ —¿
¡¡ ¡¡ ˇ ˚ ¨¡ ˇ „ ˇ –» ‡˘ ˛“ ¢æ ¨¡ ˇ „ ˇ , ¨¡ ˇ
„ ˇ ˜ ˆ ¯¯ ˆ ˇ »¥˘‰—— ˝…1 —ˆ ‰⁄ ˚ ¡£·
ˆ ¯¯ ˆ ¡¢ˆ ¯¯ •‰ˇ • – ˘‰——˜ ¨¡ ˇ „ ˇ ,‚ø —˜`¢
•‰´ ˚ˇ § ˜ ¶ ‡˘ —, ´ ˚ˇ »ø ˜ · Ni3 Ti
˛ ‡ ˇ ˜ 12 ¿ ˜ ˜ ˙ —˝¡£« · ˝…1 ( b) ¸ø ˚ ˜ ´
˚ˇ º Ni3 Ti ˛ ‡ ˇ ‚· ”ˇ ˘ ¿ ¿· ‡ : ´
˚ˇ º Ni3 Ti ˛ ‡ ˇ fi …· ` » ˛» ˇ „ ˇ ,…·:
{110}M/ / {0001}Ni
3
Ti ¡¢ < 001 > M/ / < 1210 > Ni
3
Ti ¡£
º Suk Fe210Cr210Ni22W ‚ — ˆ ‰ ˜ ‰Æ„ß ˛˙
”ˇ
[ 5 ]
, ¨¡ ˇ „ ˇ ‡˘ ˛“ ¢ ¨¡ ˇ „ ˇ ,« · ¶ ˚ ˛˜
ˇ ,¨ Vasudevan –¤…˜ ‰Æ„ß ø ˛“ ¢æ ˛» ˇ „
ˇ
[ 3 ]
, ¢æ¡¢¢`‰ ¨¡ ˇ „ ˇ — ,ˆ ¯¯ ˆ ø ˘‰——,…·
{110}M/ / {0001}Ni
3
Ti , « ˆ ¯¯ •‰ˇ †»˝‹ ¡£˛“ `¸ ¯—¶¤
ˇ ˚ ´ ˚ˇ »ø / Ni3 Ti ˛ ‡ ˇ fi …ˆ ¯¯ •‰ˇ ˜
˛– , ”ˆ ˜ •¤ ˚˙ „ † …¨”‹ — { 100}M , ”‹ —
{111}M ˜ »¤ ø ,…·» —¨º ˚ł ˘‰——
[ 011 ]M § ·ł Æ ˙Ø ¿ ˇ´ ˜ ´œ ª ¸ø „ † ˜ ı … ¡£ ¨ ‰
¿… ´˙ Ni3 Ti ˛ ‡ ˇ ˜ » ‚ ˙ —˝,· ˇ ˚ `‰ ˛» ˇ
„ ˇ ˇ ¨» ƒ ˆ ‰˝…2 ¸ø ˚ ˜ `‰ †»˝‹ ˜ »¤ø ¡£
· •´ ˜ »¤ø ¿ ¿· ‡ : ¢æ¡¢¢`‰ ¨¡ ˇ „ ˇ ˜
˛» ˇ † … 5¡ª15¡¡£
˝…3 ˚˙ º ˝…1 ˝‹ » ˚ ø ˆ ‰˜ TEM ˘‹ ,˝…3
( b) ¸ø ˚ ˜ ˘ ⁄ ˚ ˚ł ‰‰˘‰——´ ˚ˇ ˜
[ 011 ]M § ·ł Æ ,´¸ ‡ ´ ˚ˇ »ø ˚ł ˛“ ¨º
˚ł ‰ł——˜ ¶ ·˛ ,» ·˛ ˛“ Ni3 Ti ‰˚ …»fl
”ˇ ˛ 2 ‚ ˙ —˝˜ ‚· ”ˇ , »¤ø (˝…3 ( b) ) …ˇ
ƒ ˜ ‚ ˚ »fl(˝…3 (e) ) ⁄ ˚ Ni3 Ti ˙ —˝1 ˜ [ 1120 ]•‰
ˇ ˘‰—— [ 11 1 ]M ; ˙ —˝2 ˜ [ 1 1 2 0 ] •‰ˇ ˘‰——
[ 1 11 ]M § ˇ ,· ¶ł ⁄ ˆ ˝…2 ( b) •ß ”ˇ ˚ …˚˙Ø¿ ¡£
·¸ ´ ˚ˇ º Ni3 Ti ˛ ‡ ˇ fi …¨• ˙—˜ ˛» ˇ „ ˇ ˛“
¢æ ˛» ˇ „ ˇ ¡£
ˆ º [ 111 ]M ”˝ [ 1 11 ]M ˘‰ ——˜ Ni3 Ti (2240)
(˝…3 ( b) —…˝• ¸ø ‚ ·ƒ ) ˆ ‰ Ni3 Ti ˙ —˝1 ”˝ ˙
—˝2 ˜ ——˜ ‡¡ ˇæ (˝…3 (c) ”˝ ( d) ) ,¿ ˆ ‰» —'
“ ˜ —¯ˇ¢ : ˚ ˇ¨ , Ni3 Ti ‰˚ …»fl”ˇ ˛ ø ˛“ ‚¸ · ;
˘ ·˛ ,‚¸ ˜ ‡⁄ ¶¨ •‰ˇ • – º ´ ˚ˇ »ø ˜ [ 111 ]M ”˝
[ 1 11 ]M •‰ ˇ ¶ — (˝…3 (c) ¡¢( d) —…˝• ¸ø ‚ •‰ˇ ) ¡£
º ˝…1 (c) ˜ ‡¡ ˇæˇ –¨ ,˝…3 (c) ¡¢( d) ¸ø ˚ ˜ ‚¸ ·
Ni3 Ti ˜ ‡⁄ ¶¨ ‰ˇ‡⁄ ,¶ł ˙ · ¸ø —˝ ‚ ˚ § ·ł Æ „ † ,
Ni3 Ti ‚¸ ˜ ‡⁄ ¶¨ ‡⁄ , ¸ ˆ Ni3 Ti ¯ ´ ˚ˇ »ø
˜ {111}M •‰ ˇ ‡⁄ · ¡£
˛“ ‰ł » †‰ ⁄ ˚ Ni3 Ti ˛ ‡ ˇ º ´ ˚ˇ »ø ˜ ˛»
ˇ „ ˇ ,¡ ¨¡ ¨º ˚ł º [ 011 ]M § ·ł Æ ˇ ·„ – ˜
[ 211 ]M ‰ł ——„ † (˝…4) ,¿ ¿· ‡ : Ni3 Ti ˙ —˝2
†»´œª Bragg ı …,‚· ”ˇ ˘ (˝…4 ( b) ) —‰
· Ni3 Ti ˙ —˝1 ˜ , ·˛ ⁄ ˆ Ni3 Ti º ´
˚ˇ »ø fi …· ¢æ ˛» ˇ „ ˇ ¡£
ˇ ˚ · [ 011 ]M ”˝ [ 211 ]M `‰ ‚ § ·ł Æ „ † ‰ ´
˚ˇ º Ni3 Ti ˛ ‡ ˇ fi …¨• ˙—˜ ˛» ˇ „ ˇ ˛“ ¢æ
˛» ˇ „ ˇ ,˝…3 ( b) ˜ • ˛ ⁄ ˚ ¢ ¨¡ ˇ „ ˇ
†¢†» · , ‚ø ˝… 2 ˜ •´ • ˛ , [ 100 ]M º
[ 1210 ]Ni
3
Ti fi … ˇ † 5¡ª15¡ , ·¸ ,˝…1 ( b) ˆ ‰¶ ‡˘
Ni3 Ti ˛ ‡ ˇ ˙Ø¿ ˇ´ ,´ ˚ˇ »ø ª †»¶ ‡˘ ;
¶ł ´ ˚ˇ »ø ª ¶ ‡˘ ˙Ø¿ ˇ´ ,„ † †»‰ Ni3 Ti ˛
‡ ˇ ˜ ª ,‰˜ „ † ‰´ ¢ ˇ , —'⁄ ‡ • ¸ ˆ
[ 1210 ]Ni
3
Ti § ·ł Æ º [ 100 ]M § ·ł Æ »¥ †» ˘‰ —— , ´
(a) < 111 > M/ / < 1120 > Ni
3
Ti ; ¡¡ ( b) < 001 > M/ / < 1210 > Ni
3
Ti
˝… 2 ¡¡ ‚ø †»˝‹ ˜ ¨¡ ˇ „ ˇ ˜£ ˜ ˜ [ 011] M ˘
Fig. 2 ¡¡ Simulated electronic diffraction diagrams of [ 011] M according to different relationships
¡⁄ 3 8 ¡⁄
Menu
43
(a) ˆ ‡¡ ˇæ ; ¡¡ ( b) (a) ˜ ¡ ˙ł »¤ø ; ¡¡ (c) ˆ (2240)
Ni
3
Ti ˆ ‰ ˜ Ni3 Ti ˙ —˝1 ˜ ——˜ ‡¡ ˇæ ;
(d) ˆ (2240)
Ni
3
Ti ˆ ‰ ˜ Ni3 Ti ˙ —˝2 ˜ ——˜ ‡¡ ˇæ ; ¡¡ (e) »¤ø ‚ ˚ »fl
˝…3 ¡¡ › – —˛70 %¡¢510 ¡ –£˛´ 24 h ˚ ø ˜ TEM ˘‹
Fig. 3 ¡¡ Diagrams of the specimen cold rolled with 30 %reduction rate aged at 510 ¡ for 24 h, TEM
˚ˇ ˜ ‚¸ · „ º –¡ ˜⁄ ·„ – ( „ ‚¸ ˘‰——
[ 100 ]M § ·ł Æ ) , ¨ º Ewald ˙ ˇ ‰, ·¸
[ 1210 ]Ni
3
Ti § ·ł Æ º ¨º ˚ł »ø – ˘‰ ——¡¢ˆ ‰
Ni3 Ti ˛ ‡ ˇ ¶ ‡˘ ˘ ˜ ˙Ø¿ ˇ´ , ¨ —´ ˚ˇ ˜
„ ‚¸ º Ewald ˙ ˇ ‰, ˆ ‰˝…1 ( b) ¸ø ˚ ˜ †»
¶ ‡˘ [ 100 ]M § ·ł Æ »¤ ø ; ˇ •· ,‚¸ · Ni3 Ti ˛
‡ ˇ „ ª —˛· ˚˙ – · ˜
[ 6 ]
, ¨º ˚ł º
[ 100 ]M § ·ł Æ »ø – ˘‰ ——˚– ,– —˛˜ Ni3 Ti º Ewald
˙ ˇ ‰ˆ ‰´ ¢ ı ˛˘ (˝…1 (d) ) ¡£
3 ¡¡ ‰Æ´
(1) Custom 465 ‚ › „ 510 ¡ ˚– —§” , Ni3 Ti
˚˙ “ ˜ ˚– —§˛ ‡ ˇ ¡£
(2) · [ 011 ]M ”˝ [ 211 ]M § ·ł Æ »¤ ø
⁄ ˆ : (011)
M/ / (0001)
Ni
3
Ti ¡¢ [ 111 ]M/ / [ 1120 ]Ni
3
Ti …
ˇ „ ˜ ˛» ˇ „ ˇ ˚˙ ´ ˚ˇ ”˝ Ni3 Ti ‰˚ …»fl”ˇ ˛ ¨•
˙—˜ ˛» ˇ „ ˇ , ˛» ˇ „ ˇ ˚„ Ni3 Ti ´ ˚ˇ »ø
˜ ‡ ˇ 12 ¿ ˜ ˜ ˙ —˝¡£
¡⁄ 4 8 ¡⁄
Menu
3 ˘ ‡´ …˛ ¨ :´ ˚ˇ ˚– —§†»—‚ ˚– —§˛ ‡ ˇ …˛» ˇ „ ˇ ˜ —¿
(a) ˆ ‡¡ ˇæ ; ¡¡ ( b) (a) ˜ ¡ ˙ł »¤ø ; ¡¡ (c) ˆ (2240)
Ni
3
Ti ˆ ‰ ˜ Ni3 Ti ˙ —˝1 ˜ ——˜ ‡¡ ˇæ ; ¡¡ (d) »¤ø ‚ ˚ »fl
˝…4 ¡¡ › – —˛30 %¡¢510 ¡ –£˛´ 24 h ˚ ø ˜ TEM ˘‹
Fig. 4 ¡¡ Diagrams of the specimen cold rolled with 30 %reduction rate aged at 510 ¡ for 24 h, TEM
¡¡ ¡¡ (3) ”˝ ‡¡ • ˛ – ˆ ,Ni3 Ti ˛ ‡ ˇ ˛“
‚¸ · ,‚¸ ˜ ‡⁄ ¶¨ •‰ˇ º ´ ˚ˇ »ø ˜ [ 111 ]M •‰ ˇ »
´ ¡£
†˛ ¿…˛˜ ˇ :
[ 1] ¡¡ Ping D H , Ohnuma M , Hirakawa Y,et al . Microst ruct ural E2
volution in 13Cr28Ni2215Mo22Al Martensitic Precipitation2
Hardened Stainless Steel [J ] . Mat erial s Science and Engineer2
ing ,2005 , 394A :285.
[ 2] ¡¡ ¡¡ Ø“ ,‡´ …˛ ,`œ‰œˆ . Custom 465 ´ ˚ˇ ˚– —§†»—‚ ˜ ˙¿
¨˝ »fl …„⁄ ¯ »fl[J ] . ˛ † ˚ ,2005 ,23 (6) :4.
[ 3] ¡¡ Vasudevan V K, Kim S J , Wayman C M. Precipitation Reac2
tions and St rengt hing Behavior in 18 Wt Pct Nickel Maraging
Steel s [ J ] . Metall urgical and Material s Transactions , 1990 ,
21A(10) : 2655.
[ 4 ] ¡¡ HE Y, YANG K, SHA W. Microst ruct ure and Mechanical
Properties of a 2000 MPa Grade Co2Free Maraging Steel [J ] .
Metallurgical and Material s Transactions , 2005 , 36A ( 9 ) :
2273.
[ 5] ¡¡ Suk J I , Hong S H , Nam S W. Crystallographic Orientation
Relationships Among Ĥ2Ni3 Ti Precipit at e , Reverted Austen2
it e , and Martensitic Mat rix in Fe210Cr210Ni22W Maraging
Steel [ J ] . Metallurgical and Material s Transactions , 2005 ,
24A(12) : 2643.
[ 6] ¡¡ `ı ˛˜ ˛ ,»˘ —¢ł ,‡´ æ ¨ . †˜ `ˇ ‰Æ„„ ˇ ˛¢ • ˛ [ M] . ‰:
‰· § ‡ ,1989.
¡⁄ 5 8 ¡⁄
Menu
12 ¡¡ 1 ˘
2 0 0 4 ˜Œ2 ´
¡¡
†˜ ¡¡ `ˇ ¡¡ ¿˘ ¡¡ § ¡¡ º ¡¡ „⁄ ¡¡
MATERIALS SCIENCE & TECHNOLOGY
¡¡
Vol112 No11
Feb. , 2004
¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡
˛ ´ ˚ˇ ˚– —§ ‚ ˜ — ¿ ˇ ·
‰“ ¡¡ ‰ , ·
(„ ¶ß–ı „⁄ · § †˜ `ˇ ¿˘ § º „⁄ ‡ § ” ,” `œ‰›„ ¶ß–ı 150001 , E2mail : jiangyue @hit . edu. cn)
“ ¡¡ “ : ˚ `¸ ˛ ´ ˚ˇ ˚– —§‚ ˜ •¢ „ ”˝ —¿ ˇ · ,†ß˚ `¸ ˛ ´ ˚ˇ ˚– —§‚ ˜ ˚– —§Ø fl ‰Æ„„ …˙¿ »fl»œ
˘ ,• ˛ `¸ ”ˇ ‰“ ¸ ´ ˚ˇ ˚– —§‚ —˜ ˆ ,†¢Æ ‡ `¸ ˛ ´ ˚ˇ ˚– —§‚ ˛· · ˜ •¢ „ ˙ ˚˘ .
„ …·˚ : ˛ ´ ˚ˇ ˚– —§‚ ;`ƒ § —˜ ;˛ ‡ ˛ ;˙¿ »fl»œ˘
—˝…• ”¯ : TG142 ˛˜ ˇ –Œ˚¶ ´º : A ˛˜ ´ – ”¯ : 1005 - 0299(2004) 01 - 0108 - 05
Present status of cobalt2free maraging steel
J IAN G Yue , YIN Zhong2da
(School of Materials Science and Engineering ,Harbin Institute of Technology , Harbin 150001 ,China ,E2mail : jiangyue @hit . edu. cn)
Abstract : The development and research stat us of cobalt2f ree maraging steel was reviewed wit h illumination
of aging microst ruct ure and st rengt hening mechanism. The effect of t he alloy element s on t he maraging
steel were analyzed. And t he development tendency of cobalt2f ree maraging steel is forecast as well.
Key words : cobalt2f ree maraging steel ; mechanical property ; precipitation ; st rengt hening mechanism
˚ ‚ ¨ ˘ : 2002 - 05 - 13.
…‰Ø: ‰“¡¡ ‰ (1963 - ) ,˜—,‚ …¶„⁄ ‡ ˚ƒ ,†' ˚¿ œ ;
—· (1937 - ) ,˜—,‰˚ ,†' ˚¿ œ …˚ƒ .
¡¡ ¡¡ ´ ˚ˇ ˚– —§‚ ˚˙ 60 ˜Œ·œ „œ…˚˜ł „«¸ ( IN2
CO) ¿“ •¢ ˜ —´—˝‡‹ ‚ ˙¿ ¶¨ ‚
[ 1 ]
,˘ —‚ ˙¿ ¶¨
”˝ ‚ ¨˝ —˜ ˝‹ ˚– , —`…”ˆ ˜ ¡¢¨¨ …„⁄ —˜ ”˝
`…”ˆ ˜ ¿ ”‚ —, ·¸ „ª •” ƒ ˆ ”‰¿ ¡¢”‰ ¨ …¶¸
`
[ 2 ]
. ˜¿ ˙ „ª •” ƒ ˆ ˜ ˚˙ 18Ni —˝´ ˚ˇ ˚– —§
‚ ,˘ ˙¿ ¶¨ ˛“ 1 400¡« 2 500 MPa
[ 2 ,3 ]
, “ ˜ ”ˇ ‰
“ ¸ ˛“ Ni ¡¢Co ¡¢Mo ¡¢Ti ¨ . ¸ ¯ ˙¿ ¶¨ …¶– ˜ Æ ‚ ,
´ ˚ˇ ˚– —§‚ —”ˇ ‰“ ¸ `¿ ‡‹ „ 40 % , ˘ —
Co ¡¢Ni ”‹ `¿ fi ”˝ 26 %¡« 30 %. ˚„ ˆ ´ ˚ˇ ˚–
—§‚ ˜ …‚æ” „ . ¨ ˘ ‰ 20 ˜Œ· , ˛“ ‰´ “ ¸
Co ˜ ˚ · ¶ ¨– , ˚„ ´ ˚ˇ ˚– —§‚ ˜ œ †œ‡ – ·
•ø ¶¨ …,˘ ƒ ˆ ”˝ •¢ „ ˚ ‰`¸ …«· ˜ ˇ ˘ . ·¸
´ ˚ˇ ˚– —§‚ —¿ ˜ » ‚ “ •‰ˇ ˝ ˚˙ •¢ „ ˛
´ ˚ˇ ˚– —§‚ . ˜¿ ˙ „œ˝ —¿ ”˝ ¿“ •¢ ‡ ¶ ˛
´ ˚ˇ ˚– —§‚ , †¢‡ „ƒ ƒ ˆ „ …†¿ …
[ 4 ]
. —
¿ ‰ˇ¶ ˜ ˚˙ T - 200¡¢T - 250¡¢T - 300 —˝(˙ ” T
– ˚ Ti ˙¿ »fl‚ ) ˛ ´ ˚ˇ ˚– —§‚ ,« ˙¿ »fl˜
˛ ´ ˚ˇ ˚– —§‚ ˙¿ ¶¨ · ‰‰ˇ‚ ¸fi ˘‰˚– ,¸ —¡¢
¨˝ —…– ˇ´ ‰
[ 2 ]
. ¨ ”˛ Æ ‚ ˛ ´ ˚ˇ ˚– —§‚ ˜
¸ —”˝ ¨˝ —˚˙ » ‚ “ ˜ —¿ •‰ˇ . – ˛˜ ‰«· ˛
´ ˚ˇ ˚– —§‚ ˜ ‡ • ¡¢Ø fl ‰Æ„„ ¡¢—˜ ¡¢˙¿ »fl»œ
˘ ¨ ¶ •‰ˆ •· ‡ ˛ ´ ˚ˇ ˚– —§‚ ˜¿ ˙ ˜ —¿ ·
¿ .
1 ¡¡ ˛ ´ ˚ˇ ˚– —§‚ ˜ ¿“ •¢ ¡¢‡ •
º `ƒ § —˜
¡¡ ¡¡˛ ´ ˚ˇ ˚–—§ ‚ ˜ —˘ ˚… ˆ „œ,„œ…˚˜ł
„«¸ ( INCO) º Teledyne Vasco „«¸ ”ˇ ,¿“ •¢ `¸
T - 250 ˛ ´ ˚ˇ ˚– —§‚
[ 4 ]
. º 18Ni ´ ˚ˇ ˚–
—§‚ ˇ –¨ ‰ˇ, T - 250 ‡ • —˝Œ¨« ¨¥ `¸ Co ,‰˝
`¸ Mo ˜ ”‹ `¿ , …`¸ Ti ˜ ”‹ `¿ . ˝¤ „ ß Ti ”‹
`¿ ,‰ł» †‰¿“ •¢ `¸ T - 200 ”˝ T - 300 ˛ ´ ˚ˇ
˚– —§‚ ,˘ —˜ ˇ – ˇ ƒ …¶– ˜ ”‹ 18Ni ´ ˚ˇ
˚– —§‚ . º ·¸ ˝‹ ˚– ,¨ – ¡¢”«„œ¡¢¡ ¶¨ ¨ „œ† ˇ …
¿“ •¢ `¸ ˛ ”‹ ‚ı ¡¢˛ ”‹ ˛ ¡¢˝ ˜ł ˛ ´ ˚ˇ ˚–
—§‚
[ 5¡« 7 ]
. ˛ „œ ˛ ´ ˚ˇ ˚– —§‚ •‰ˆ † ‰ł——
`¸ » —'—¿
[ 8¡« 11 ]
.
ˇ ˚ ˛ ´ ˚ˇ ˚– —§‚ ˜ ˙¿ ¶¨ º ”‹ ´ ˚ˇ
˚– —§‚ ˇ – ,—˜ ı ` ‡‹ „ ”‹ ´ ˚ˇ ˚– —§‚ ,¶ł
¸ ¡¢¨˝ —‚ . – 1 ¡¢– 2 • – ‚ł ‡ `¸ » —' —˝˛
´ ˚ˇ ˚– —§‚ ˜ »fl§ ‡ • ”˝ `ƒ § —˜ .
Menu
1 ¡¡ ˛ ´ ˚ˇ ˚– —§‚ ˜ ‡ • ( ˚ `¿ • ˚ / %)
[ 4¡« 12]
†˜ ¡¡ `ˇ Ni Mo Ti Al Cr ˘ ¸ß †œ
T - 250 18150 3100 1140 0110 - - ˆ „œ
T - 300 18150 4100 1185 0110 - - ˆ „œ
W - 250 19100 - 1120 0110 - 415W ”«„œ
14Ni - 3Cr - 3Mo - 115Ti 14131 3124 1152 - 2188 - ¨ –
12Ni - 312Cr - 511Mo - 1Ti 12100 5110 1100 0110 3120 - ¡ ¶¨
Fe - 15Ni - 6Mo - 4Cu - 1Ti 15100 6100 1100 410 —„œ
Fe - 8Ni - 3Mn - 5Mo 7180 4180 0150 0120 01005Ce —„œ
Fe - 18Ni - 4Mo - 117Ti 18100 4100 1170 —„œ
– 2 ¡¡ ˛ ´ ˚ˇ ˚– —§‚ ˜ `ƒ § —˜
[ 4¡« 12]
†˜ ¡¡ `ˇ ƒ
b
/ MPa ƒ
s
/ MPa ƒ˜ / % ƒ / % HRC K
¢æC
/ ( MPa¡⁄ m
1/ 2
)
T - 250 1817 1775 1015 5611 5018 106
T - 300 2100 2050 10 54 5316 76
W - 250 1800 1780 9 45
14Ni - 3Cr - 3Mo - 115Ti 1820 1750 1315 6510 5110 130
12Ni - 312Cr - 511Mo - 1Ti 1700 1660 10 102
Fe - 15Ni - 6Mo - 4Cu - Ti 1893 1785 915 46 5215
Fe - 8Ni - 3Mn - 5Mo 1545 1485 14 4012
Fe - 18Ni - 4Mo - 117Ti 2000 9 70
18Ni250 (”‹ ‚ ) 1830 1710 1216 7018 5110 137
2 ¡¡ ˛ ´ ˚ˇ ˚– —§‚ —”ˇ ‰“ ¸ ˜
ˆ
¡¡ ¡¡º ”‹ ´ ˚ˇ ˚–—§ ‚ ˇ –¨ ,˛ ‚ ˜ »fl§ ‡
• —‡ `¸ Ni ¡¢Co ¡¢Mo ¡¢Ti ”ˇ ‰“ ¸ ˜ ”‹ `¿ – »fl˝ ,
†»˝‹ ˜ ‚ …`¸ ` ˝ » —'˙¿ »fl“ ¸ ,¨ Cr ¡¢W¡¢
Mn¡¢Cu ¨ ”ˇ ‰“ ¸ .
”‹ ´ ˚ˇ ˚– —§‚ — , ¸ „ ¨ »ø «
†¢†»—˛‡ ‰˚ …»fl”ˇ ˛
[ 12 ,13 ]
,¶ł º †œœ —› —§
ƒ (synergistic effect )
[ 1 ]
. ˘ ˆ …ı ´
˚ˇ —˜ „ ¨ ¶¨ ,· ¶ł · ‰ł”‹ ‰˚ …»fl”ˇ ˛ ˜
˛ ‡
[ 14 ]
;` ˝ , ¿ ˘ ´ ˚ˇ —˛» · ˙ ‰Æ„„
˜ » ‚· ,˛“ ¸ ” ˜ ˛ ‡ ˇ —˛‡ Æ „' ‚ ¶ ˜ —˛”¸ ˛»
ˆ ,˚„ ˛ ‡ ˇ `£ ‚ ˛“ ˇ‚ —¡¶ł • †…ø ¨ . ¨» ¶ł
†¢†»¸ ˆ ˜ ‰»»¥ ˆ ¶ ¨˝ ——„– ˇ ,` ‰æ»„
ˆ» —˚ Ø ˚ ⁄ ˆ Æ ‚ ˙¿ ¶¨ ˜ ˝‹ ˚– —‚˜ ˘
¨˝ —˜ ˆ . ·¸ ,´ ˚ˇ ˚– —§‚ —…·˚„ †»”‹ ,
† †»» ¶¤»Æ…´ ¸ ¨˝ —¶æ»fl.
´ ˚ˇ ˚– —§‚ —`…”ˆ ¨˝ —˚˙ »ø —”‹
—‰ˇ¶ ˜ł ˜ „˚ . ˜ł ˚˙ ´ ˚ˇ —˛‡ “ ¸ ,˜ł ˜ ·
' · `¸ ´ ˚ˇ ˙ł ,‚ …¨¨ ˚– »æˆ ¥ ˇ ´ ˚ˇ ,
–‚ ¨· ˚– »æˆ —`…”ˆ •¶ —˜ ´ ˚ˇ . ˝‹ ˚– ,˜ł
˜ · ‰˝ Ms ª . ˜ł ˚˙ ´ ˚ˇ ˚– —§‚ — “ ˜ ˛
‡ ˇ —˛‡ “ ¸ . ´ ˚ˇ ˚– —§‚ — ,˜ł º ˙¿ »fl“ ¸
‰Æ”ˇ —˛‡ ˙¿ »flˇ ,…¨º ˙¿ »fl“ ¸ “ ˇß ”˜ ˜ł ,¨ »ø
—˜ł ”‹ `¿ ˝ 10 % , »Æ ˘ ¨˝ —ˇ´ ‰. ¶ ˛
‚ ,˛“ –£⁄ ‚ ˜ ˙¿ ¨˝ —,˜ł ¡¢ ¡¢ 3 “ ¸ ”‹ `¿ ƒ ¿
˘ » ¶¤”‹ `¿ •¶ ˛§ fi ˜
[ 15 ]
. ¸ ¨» ˜ł ˚˙ Æ ‚ ¨˝ —˜
——§“ ¸ ,« ˆ» —– “ …¨º „ ¶ ˜ ˜ł ,¨ ˜ł ”‹ `¿ „
¶ ,Ms ª ‰˝ , ¨· ˚– »Æ…´ †— ´ ˚ˇ ˜ —˛‡ ,
· ¶ł ˚„ ˚– —§” ˜ ˙¿ ¶¨ ‰˝
[ 16 ]
.
´ ˚ˇ ˚– —§‚ —¶ ˙¿ ¨˝ —¶…—ß ˜ ”ˇ ‰“
¸ ˚˙ . ˚– —§‡ı ˘ ˛ ‡ ˜ ‚» ˛ ‡ ˛ , ˙¿ »fl˜ ˝‹
˚– –£‡ ‚ ˜ ¨˝ ——˘ ¯ “ ˆ
[ 17 ]
. ˝‹ ˚– † ¿
Ł „ ˛ ‡ ˇ › ´ ˚ˇ § ‰˛ ‡
[ 18 ]
,· ¶ł – ˆ
`¸ § ¶ˇ ` ¡¢Æ ‚ `¸ ¶ˇ ` ¨˝ —. « „ `¿ … †
»Æœ ‡ †— ´ ˚ˇ . 18Ni ˇ ´ ˚ˇ ˚– —§‚ —
˜ ˚ `¿ • ˚ ƒ ¿ ˘ 8 % ˇ´
[ 19 ]
. ¶ ˛ ´ ˚ˇ
˚– —§‚ , ˚§ ¨¥ `¸ ¡¢ ˜ ‰»»¥ ˆ ,‚» ˛
‡ ˛ ˜ ˛ ‡ `¿ ˇ ¶ ‰˝ ,˚„ ˙¿ »fl—§„ß…ı¨ı . « ¨ „ß
˛“ …˙¿ ˜ ˙¿ »fl ˆ ¶ł … ”‹ `¿ , ‚ —
—˛‡ ‚ ˛´ „ ¨ ˚– ¶…†» ¨ ‰˜ ‚» ‰˚ …»fl”ˇ
˛ ,˝‹ ˚– † ¿ ˜ …´ †— ´ ˚ˇ ˜ —˛‡ ,· ¶ł ˚„ ‚
˜ ¸ ¡¢¨˝ —ˇ´ ‰, ·¸ †»˜ ˝¤ „ … ”‹ `¿ –£‡ ˙¿
¡⁄ 9 0 1 ¡⁄
1 ˘ ‰“¡¡ ‰ ,¨ :˛ ´ ˚ˇ ˚– —§‚ ˜ —¿ ˇ ·
Menu
. ˛˜ ˇ [ 10 ]‚ ‡ , ”‹ ˝› ˛ ´ ˚ˇ ˚– —§‚
— , ˜ ˚ `¿ • ˚ · 7 % ,‡ » ¨˝ —ˇ ł ‰˝ .
˛ ´ ”‹ »„ ˚˙ ˛ ´ ˚ˇ ˚– —§‚ — , ¶…
˚˙ — —§˜ ˙¿ »fl“ ¸
[ 17 ]
. ˛ ‚ — , ˆ¿ …
011 %˜ , ˙¿ ¶¨ … 54 MPa
[ 7 ]
. « ˙¿ »fl ˜
Fe - Ni”ˇ ‰ ˙¿ ¶¨ · ‰‰ˇ‚ ¸fi ˘‰˚– ,¨˝ —ˇ ¶æ
»fl. ·¸ , …¨º `¿ “ —» ¶¤ˇ ˘ . Tharian ¨ˇ ˛“
˛ ´ ˚ˇ ˚– —§‚ — ”‹ `¿ ( ˚ `¿ • ˚ ) · ˛“
110 %
[ 7 ]
. T - 250 ‚ — ˜ ˚ `¿ • ˚ ˛“ 114 % ,
º C - 350 ”‹ ´ ˚ˇ ˚– —§‚ — ”‹ `¿ ˇ – ;
T - 300‚ — ˜ ˚ `¿ • ˚ ‚ · 1185 % , ¸ ˆ
˝¤ „ … ”‹ `¿ •¢ „ ‚ ‚ …¶– ˜ ˛ ´ ˚ˇ ˚– —§
‚ ,– ‰« ˘ ¸ ¡¢¨˝ —˜ ˇ ˇ´ ‰. ·¸ ƒ ˙ ß
ˆ ˘ ¸ß ”ˇ ‰“ ¸ · •¢ „ ‡‹ ‚ ˙¿ ¶¨ ˜ ˛ ´ ˚ˇ ˚–
—§‚ .
Fe - Cr - Ni ¨ “ ”ˇ ‰ˇ — , Cr ˜ · ‰ł´
˚ˇ ˇ ˜ —˛‡
[ 18 ]
. ·¸ , ˛ ´ ˚ˇ ˚– —§‚ — ,
‚ı ¿ ·œ†¿• ˜ł
[ 5 ,7 ]
. ——¿ – ˆ “ ˆ ‰`…”ˆ ¨˝
—,` —Ł“ 17 %(Ni + Cr) (˚ `¿ • ˚ ) ,“ –£⁄ ˆ
‰ · ˙¿ ¶¨ , 17 %¡« 21 % ( Ni + Cr) ˚˙ ·
[ 20 ]
.
˙‡ ‰——¨ ‚ ‡ : 14Ni - 3Cr - 3Mo - 115Ti ‚ — ,
˛“ »æˆ `…”ˆ ¨˝ —,` —Ł“ (12 %¡« 14 %) Ni + 3 %
Cr (˚ `¿ • ˚ ) …ı Ni Ti ˛ ‡ ˘ »ø —˘¶ ˜ł
¶ł ‡ ˜ ¨˝ —¸ ˚§
[ 5 ]
. ˝ ˜ł ˛ ´ ˚ˇ ˚–
—§‚ — ,˜ł ”‹ `¿ ‰˝ ,Ms ª ‚ ,„ ¨ ·ƒ ¨· „
‡ ——¿ ˜ †œœ ˛ ‡ ˇ , ¶ ¨˝ —†»ß , ·¸ …¨º
Cr ‰˝ Ms ª . ‚ı »„ ¿ ˜ ˝¤ „ ¿ ˘ ˜ ˛ ‡ •·
ƒ · Æ ‚ ¨˝ —. Fe - 14Ni - 115 Ti - 3Mo‚ — ,
Ø ¸ …3 %Cr ¿ ——§ • „ Ti ˝ ˛´ ˇ ˛ ‡
˘ ˜ · »fl ,« …‚ı • „ · »fl ,» —˜ł ˜ ˚ `¿ •
˚ ‚ 12 %˚– †¯ ——§„ß
[ 21 ]
. ˚´ ˚ ˇ , ‚ ˜ Cr/ Ni
–¨ ¶ Fe
2
( Mo , Ti) ˜ ˛ ‡ –¨ Ni
3
Ti ‚ ˛“ —ß ,· ¶ł
˚„ ‚ ¶ ˜ ˜ł –£` »ø — ,« “ ˙ „ ¨ ·ƒ
”˝ ˚– —§„ ‡ —” ”ˆ ¿ ˘ , –£⁄ œ ‡ ˇ‚ —¡˜ Fe
2
(Mo , Ti) ˚ ª
[ 20 ]
.
·« ˝‡ ˜ ´ ˚ˇ ˚– —§‚ — ,Mn » – ˚˙ ˛“
˚ “ ¸ ¶ł · ˜ ,˘ ”‹ `¿ (˚ `¿ • ˚ ) ˚ ‰`¸ ˇ ‚æ
˜ ¿ ˘ ( ¡ 011 %) . †»„ , Fe - Mn ˇ ”ˇ ‰
— ,¿ ‰ˇ¿ ˜ ¨· ¸ ¶¨ •¶ ˛§ ˜ —˛‡ ı » ¿Ø
· ´ ˚ˇ Ø fl ,¸ø Fe - Mn ”ˇ ‰† ˛“ ˚– —§˙¿ »fl
Æ„' `¸ `…”ˆ ˜ »ø·¡ . Mn ˚˙ ' · ƒˆ ˙ł ˜ “ ¸ , ‚
— Mn ˜ ˛¨ ¶¤´ ˚ˇ Ø fl ˜ ˜ `ƒ ‰·˛ Ni
[ 18 ]
.
·¸ , 18Ni ´ ˚ˇ ˚– —§‚ — , Mn ¿ †¿ • ¨¡ ·œ
Ni ”˝ Co
[ 9 ]
. ˛˜ ˇ [ 22 ] ‚ ‡ , 1 %˜ Mn ¿ ¨¡ ·œ
3 %˜ Ni ; « Mn ¨¡ ·œ Ni ‰«˚„ ”ˇ ‰¨˝ —ˇ´ ‰, Mn
¨¡ ·œ Ni ˜ `¿ †»˜ ‡‹ „ 6 % , …˜ Ni - Mn ¯ ”ˇ
· …˛“ 1215 %Ni - 2 %Mn.
´` ˝¤ ‡£˚˙ ˛“ ˝ ı …`…¨º ‰‚ —˜ . „ ´`
˜ ˆ ,– ˚ ˇ ¸ , ´ ˚ˇ ˚– —§‚ —† ¿ †œœ
† »fl ,„˚ ˛ ´ ˚ˇ ˚– —§‚ —† —ˆ ´` ˛“ ˙¿
»fl“ ¸ ˜
[ 9 ,22 ]
, †¢˙ —˛ ”‹ ´` ( ˚ `¿ • ˚ ˛“
1 %¡« 315 %) ´ ˚ˇ ˚– —§‚ ˛˚ ˚
[ 23 ]
.
ˇ¡ ˝` “ ¸ ¿ Æ ‚ ´ ˚ˇ ˚– —§‚ ˜ ¸ ¨˝ —
[ 24 ]
.
« „ ˇ¡ ˝` “ ¸ ¶ ˛ ´ ˚ˇ ˚– —§‚ —˜ •‰ˆ ˜
ˇ ,¸ø ‰ł——˜ —¿ »„–¨ ‰ˇ ,—Ł“ ‰ł» †‰—¿ .
3 ¡¡ ˛ ´ ˚ˇ ˚– —§‚ ˜ ˚– —§Ø fl
˛ ´ ˚ˇ ˚–—§ ‚ º ”‹ ´ ˚ˇ ˚–—§ ‚ »
ø ,˘ ‚ ˙¿ ¶¨ · · ˚– —§˙¿ »fl ,˝¤ „ 400¡« 500 ¡ ˚–
—§, ´ ˚ˇ »ø ˜ †œœ `¸ · `¿ ˜ ‰˚ …»fl”ˇ ˛
˛ ‡ ˛ . ˛ ‡ ˛ ˜ —˝¡¢‰Æ„„ ¶¤ ‡ • ¡¢˚– —§˛´
¶¨ ”˝ ˚– —§˚– ….
˜¿ ˙ ,—¿ ¶ ‡£„ ˚„ ˆ ˜ Fe - Ni - ( Co) -
Mo - Ti ´ ˚ˇ ˚– —§‚ ‰ł——`¸ · `¿ ˜ —¿ ,« „
˛ ‡ ˇ ˜ ”˝ ˘ ˛ ‡ „ ‡ ——” · ø Ø . †»
˝‹ ˜ —¿ ˝‹ » ‚ —¸ø ˆ ‰˜ ‰Æ„ß † †»¡ ˇ
˝‹
[ 4 ]
. Decker ¨ ˛˜ ˇ [ 4 ] — `¸ ‚¯ ¤ , ´ ˚ˇ
˚– —§‚ — “ ‡` ˛ ˛“ : Ni
3
M ( M = V , Mo , Nb ,
W) ¡¢ ƒ˙ - Ni
3
Ti ¡¢Fe
2
Mo Laves ˇ ¡¢†»˝‹ —˝˜ ƒ ˇ
(FeMo ¡¢Fe Ti) ¡¢ ƒ - Fe
7
Mo
6
”˝ ƒ ˇ . ¨ ‰˙§ ˇ ˜ R
ˇ † —•¢ ˇ « †»‡£…ß.ƒ˙ - Ni
3
Ti ”‹ ”˝ ˛ ‚
—¶…˚˙ “ ˜ ˛ ‡ ˛
[ 7 ]
. Fe
2
Mo ˇ ”‹ ˝ ”ˇ ‰

[ 12 ]
¡¢ ƒ - Fe
7
Mo
6
ˇ ”‹ ”˝ ˛ ‚ — ¶…— •¢ ˇ .
·¸ ˝ , ”‹ Cr ´ ˚ˇ ˚– —§‚ »„ „ † ‰ ƒ ˇ ”˝
Ti
6
Si
7
Ni
16
„Ł »fl ˛
[ 25 ,26 ]
.
¶ W - 250 ‚ ˚– —§„ ‡ ˜ —¿ –
ˆ
[ 6 ]
, “ ˙¿ »fl˛ ‡ ˇ ˚˙ ‰»‰Æ„„ ˜ Ni
3
W ˇ ”˝
`ø •‰‰Æ„„ ˜ ƒ˙ - Ni
3
Ti ˇ . Ni
3
W ˇ ˜ ¨¡ ˇ „ ˇ ˛“
{011}
M
/ / ( 010)
Ni
3
W
, < 111 >
M
/ / [ 100 ]
Ni
3
W
. ƒ˙ -
Ni
3
Ti ˜ ¨¡ ˇ „ ˇ ˛“ { 011 }
M
/ / ( 0001 )
Ni
3
Ti
, <
111 >
M
/ / [ 1120 ]
Ni
3
Ti
.
Vanderwaiker
[ 27 ]
— ¿ `¸ T - 250 ‚ ˜ ˚– —§˛
‡ „ ‡ ,•¢ ˇ ˛ ‡ „ ‡ —˚ ˇ¨ †œœ ˜ł ˘« ˛ , ˜ł
˘« ˛ ,…´ ‚» ˜ł ˙ł ‡ ˇ ˜ “ – ´ ˚ˇ , ” Ni
3
Ti
˜ “ ´ ˚ˇ ˇ ‡ ”¸ ‡⁄ · , Ni Ti ˛ ‡ ˜ —˛· ”˝ ¨¡
ˇ ˜ “ – ´ ˚ˇ ¶¤ , Ni
3
Ti ˛ ‡ ” ,†¿ • ˜ “
– ´ ˚ˇ ¿ ˜ —´“ – ‡ ´ ˚ˇ . ˛» · ”˝ § ‰
ˇ † •¢ œ ˝‹ ø ˜ •˙ ø ¨ ˛ ‡ „ ‡ . ‡⁄ · ˜
‰¶˛ ,Ni
3
Ti ˛ ‡ ˇ — ¨ ¨º `¸ » †¿ • , ·¸ ˚
…˚ˇ ˛ ‡ ˇ ˚˙ Ni
3
( Ti ,Mo) .
¡⁄ 0 1 1 ¡⁄ †˜ ¡¡ `ˇ ¡¡ ¿˘ ¡¡ § ¡¡ º ¡¡ „⁄ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ 12 ¡¡
Menu
1 1 1 ¡⁄
1 ˘ ‰“¡¡ ‰ ,¨ :˛ ´ ˚ˇ ˚– —§‚ ˜ —¿ ˇ ·
Menu
2 1 1 ¡⁄ †˜ ¡¡ `ˇ ¡¡ ¿˘ ¡¡ § ¡¡ º ¡¡ „⁄ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ 12 ¡¡
Menu
1
,ˇfl ˚ ˜–
1
,¯ ‰¤„œ
1
,˚' `
2
,£ ˚
2
(1==++≠⁄ 3÷´´2©EX©hI¥2©4´≠⁄ ≥2©5¯,´ ˛ ˛ † ¡¡ 710072; 2¯-:∂>5¯210¸ø ,´ ˛ ˛ † ¡¡ 710065)
“ “ :· ˛ ´ ˚ˇ ˚– —§‚ ˜ ¡¢”ˇ ‰»fl¡¢¨¨ ·ƒ ¶ ‚ˆ †˜ `ˇ `ƒ § —˜ ˜ ˇ …˙¿ »fl»œ ¨ •‰ˆ ˚ `¸ ˛ ´ ˚ˇ
˚– —§‚ ˜ —¿ ”˝ ƒ ˆ ‚¯ ¿ ¡£˛ ´ ˚ˇ ˚– —§‚ —†»”‹ ” „ ˜ “ ¸ ,ß ˆ ı ´ ˚ˇ »ø ˇ ˛ ‡ ˜ N i
3
( Ti,
Mo)¨ ‡` ˇ · ˚ ˇ ˙¿ »fl , ˝ 2100MPa˜ ˙¿ ¶¨ •¶ ˛§ ˜ ,º ˝‹ …¶– ˜ ”‹ ˜ 18N i´ ˚ˇ ˚– —§‚ ˇ –¨ ,—ˇ ‰˜
˙¿ ¨˝ —¡£
„ …·˚ :˛ ´ ˚ˇ ˚– —§‚ ;„ ¨ ·ƒ ;˚– —§·ƒ ;˙¿ »fl»œ˘ ;`ƒ § —˜
—˝…• ”¯ : TG14224¡¡ ¡¡ ˛˜ ˇ –Œ˚¶ ´º : A¡¡ ¡¡ ˛˜ ´ – ”¯ : 0254·6051( 2007) 02·0007·05
Research and Applications of Cobalt·Free Maraging Steels
L IU Fu·guang
1
, X I Shou·mou
1
, ZHANG J ian·guo
1
, SH I Yan·ling
2
, ZHENG Shu·li
2
(1School of Materials Science and Engineering, Northwestern Polytechnical University, Xi¡an Shaanxi 710072, China;
2The 210 Research Institute of CASIC, Xi¡an Shaanxi 710065, China)
Abstract: Research and applications of Co·free maraging steels were introduced in many respects, including their kinds,
alloying, influence of solution and aging treatments on mechanical properties and the strengthening mechanism of the al·
loys. Co·free maraging steels have a good combination of ultra·high strength and moderate toughness, close to that of the
18N i maraging steel containing Co with the same strength level below 2100 MPa. The superior performance is achieved by
aging precipitations such as N i
3
( Ti,Mo) in lath martensite matrix.
Key words: cobalt·free maraging steels; solution treatment; aging treatment; strengtheningmechanism; mechanical p roper·
ties
… ‰Ø:`ı ‚£ „ª ( 1981. 04¡“ ) ,˜—,” ––ˇ ˇ ¨¸ ,¸¶ ˚¿ —¿ œ ,
“ · ˚´ ´ ˚ˇ ˚– —§‚ ˙¿ ¨˝ »fl»œ — ¿ ¡£ `“ ˇ » : 029·
88488023¡¡ E·mail: lfuguang@163. com
˚ ‚ ¨ ˘ : 2006·10·28
¡¡ ¡¡ ´ ˚ˇ ˚– —§‚ ˘ ‡‹ ‚ ˙¿ ¶¨ ¡¢‚ ¨˝ — ¡¢¯ ˜ …„⁄
”˝ ”‚ ‰—˜ ¶ł „ª •” ƒ ˆ ”‰¿ ¡¢”‰ ¨ …¶¸ `
[ 1 ]
¡£
˜¿ ˙ ƒ ˆ ‰ˇ ¶ ˜ ˚˙ ”‹ ˜ 18N i—˝´ ˚ˇ ˚– —§‚ , ˘
Co”‹ `¿ ‚ · 8% ¡« 12% ,„ ‚ ˜ ‡ – ˇ ˘ ˘ ‰ł» †‰•¢
„ ”˝ ƒ ˆ ¡£ ·¸ •¢ „ ‚ —˜ ˛ ´ ˚ˇ ˚– —§‚ ,‰˝
‡ – ˚˙ ‡‹ ‚ ˙¿ ¶¨ ‚ —¿ —˜ » ‚ “ •‰ˇ ¡£˜¿ ˙ „œ˝
¿“ •¢ ‡ ¶ ˛ ´ ˚ˇ ˚– —§‚ ,†¢ —†¿ • ˛ ‚
‡ „ƒƒ ˆ „ …†¿…, ¨ ,ˆ „œ ‰«T250˛ ´ ˚ˇ
˚– —§‚ ‡ „ƒƒ ˆ TOW¡¢Stinger¡¢AMRAAM…fl ,
ˆ ˙Æ—˝„¥» ˙¯ ¡¢„ ˜£ ¡¢¢ ¸ ˜£ ¡¢• ¶· Ł –‚ ¨
[ 2 ]
¡£ ˛ „œ ¶
˛ ´ ˚ˇ ˚– —§ ‚ ˜ — ¿ ”˝ ƒ ˆ »„ ” ,– ˛˜ ˝¤ „ ‚¯ ˚
• ˛ ˇ —˛ ´ ˚ˇ ˚– —§‚ ˜ —¿ ‡ „ß ,ˇ£ ˝ß ˜ „»˝˘ ¶fl
˛ ´ ˚ˇ ˚– —§‚ ˛ „œ‚ ……˚ı ` ˜ ƒ ˆ ¡£
1¡¡ ˛ ´ ˚ˇ ˚– —§‚ ˜
– 1`—‡ `¸ » —' —˝´ ˚ˇ ˚– —§‚ ˜ ‡ • …˘ `ƒ
§ —˜
[ 1¡« 11 ]
¡£ ¿“ •¢ ‡ „ƒ ˜ ˛ ´ ˚ˇ ˚– —§ ‚ ˚˙
”‹ 18%N i˜ T250—˝˛ ´ ˚ˇ ˚– —§‚
[ 4 ]
, „œ…˚˜ł
„«¸ ( INCO)º Teledyne Vasco„«¸ ”ˇ —˘ ,˘ — T
– ˚ ˙¿ “ ¸ ˛“ Ti¡£º C—˝”‹ ˜ 18N i (250)´ ˚ˇ
˚– —§‚ ˇ –¨ ,¸ ˆ˙ ˜ `ƒ § —˜ ˇ ‰,¶ł T250˛ ´ ˚ˇ
˚– —§‚ ˜ ‡ • —†»”‹ “ ¸ ,‰˝ `¸ ”‹ `¿ , …`¸
”‹ `¿ ¡£˝¤ „ ß ”‹ `¿ , —˘ ‡ `¸ T200…ƒ
02

‰ 2000 MPa˜ T300˛ ´ ˚ˇ ˚– —§‚ ¡£º ·¸ ˝‹ ˚– ,
”«„œ
[ 6 ]
— ˘ ‡ `¸ ˆ W ·œ Mo˜ W250˛ ´ ˚ˇ ˚–
—§‚ , ˘ ƒ
02
º T250 ˇ – , ¶ł ¸ ¨˝ — ‰ˇ˝ ¡£ ¨

[ 7, 12 ]
¡¢¡ ¶¨
[ 8 ]
† ¿“ •¢ `¸ ˆ †¿ • ‚ı ·œ ˜ł ˜ ˛ ´ ˚ˇ
˚– —§ ‚ ¡£ ¨ – ˜ ˛ ´ ˚ˇ ˚– —§ ‚ ˙¿ ¶¨ º T250ˇ
– ,¶ł ¸ ¨˝ —“ ¯ T250¡£¡ ¶¨ ˜ ˛ ‚ ˙¿ ¨˝ —º
T250ˇ –¨ ˙¿ ¨˝ —˘« ˝ ¡£· – 1¿ ¿· ‡ ,˛ ‚ ˜ `ƒ
§ —˜ ¿ º ˇ ˝‹ …¶– ˜ ”‹ ‚ ˇ ˇ – ,¶ł ‡ – ¨· ‰
˝ `¸ 20% ¡« 30%¡£
˛ „œ ˛ ´ ˚ˇ ˚– —§‚ •‰ˆ † ł ¿“ „ „ —¿ „⁄
,ł —”‹ ˝› ˛ ´ ˚ˇ ˚– —§”ˇ ‰˜ –¤
[ 9 ]
,« ¸ —¡¢
¨˝ —« ˝
[ 13 ]
¡£ ‰ ”˛ ª
[ 10 ]
¨ ¨¸ ‡˘ ¿“ •¢ ‡ `¸ ˙¿ ¶¨ ‚ ·
2078 MPa ˜ —´ —˝ 18N i ˛ ´ ˚ˇ ˚– —§‚
(00N i18Mo4Ti) ,˘ `ƒ § —˜ º T300‰‰, « ‰˜¿ ˙
˛“ „ ,»„» ˚˙ ·ƒ ˚ Ø ‰¶˛ ¡£‰…‚˜Œ· , T250˛ ´
˚ˇ ˚– —§‚ † › „œ˜ —˘ ‡ „ƒ†¢ †‰˝¶ ¨º œ †œ
”˝ ˚„ ˆ
[ 14 ]
,« ˇ ˜ ¨¨ ·ƒ „⁄ »„ ” †»‡ ˚ ¡£ ¨ ,
¶ ·˛ · – —˛`¿ —„ · ‹ T250—˝˛ ´ ˚ˇ ˚– —§‚
› „ ‡£„ ¨¨ ·ƒ ” ,˘ ˙¿ ¶¨ ”˝ ¸ —†»˜ ´œª ……˚ı “ ˙ ,
˘ „⁄ ”˝ »œ ¶…—· —¿ ¡£
7
¡¶‰ ˚ ¨¨ ·ƒ ¡•2007˜Œ 32 2˘
Menu
1¡¡ „œ˜ ˝ » —' —˝´ ˚ˇ ˚– —§‚ ˜ »fl§ ‡ • ”˝ `ƒ § —˜
[ 1¡« 11]
Table 1¡¡ Chem ical composition and mechan ical properties of some typical maraging steels at home and abroad
„œ… †˜`ˇ ¯˘ ”¯
»fl§ ‡ • (wt% )
Ni Co Mo Ti Al ˘ ¸ß
`ƒ § —˜
ƒ
02
/MPa ƒ˜( % ) ƒ ( % ) K
IC
/MPa¡⁄ m
1 /2
ˆ „œ 18Ni (250) 185 75 48 04 01 - 1760 11 58 135
ˆ „œ 18Ni (300) 185 90 48 06 01 - 2000 11 57 100
ˆ „œ 18Ni (350) 185 120 48 14 01 - 2340 73 52 61
ˆ „œ T250 185 - 30 14 01 - 1750 105 561 100·123
ˆ „œ T300 185 - 40 185 01 - 1940 88 45 74
”«„œ W250 189 - - 12 01 42W 1780 90 - 100
¨ – 14Ni·3Cr·3Mo·15Ti 143 - 32 152 - 29Cr 1750 135 650 130
¡ ¶¨ 12Ni·32Cr·51Mo·1Ti 120 - 51 10 01 32Cr 1660 100 - 102
—„œ Fe·15Ni·6Mo·4Cu·1Ti 150 - 60 10 - 40Cu 1785 95 460 -
—„œ Fe·18Ni·4Mo·17Ti 180 - 40 17 - - 2078 90 - 70
¢ :˘ — W250˜ K
IC
˚˙ ˝¤ „ ˛˜ ˇ [ 11 ]‰«› ˛˜ ˇ —˜ ‡ » „ƒ‰¸˘ »»¸ª ¶ł ·
2¡¡ ˛ ´ ˚ˇ ˚– —§‚ ˜ ”ˇ ‰»fl
”‹ ´ ˚ˇ ˚–—§ ‚ —, ¸ „ ¨ »ø « †¢†»
—˛‡ ‰˚ …»fl”ˇ ˛
[ 15·16 ]
, ¶ł º †œœ —›˝‹ —§ƒ
[ 17 ]
( synergistic effect) , · ‰ł”‹ ‰˚ …»fl ”ˇ ˛ ˜ ˛

[ 18 ]
,· ‰˙¿ »fl—§„ß ¡£` ˝ , »„ ¿ ˇ ˛» · ˙ ‰Æ
„„ ,˛“ ˛ ‡ ˇ Æ „' ø ¨ ˜ —˛”¸ ˛» ˆ ,· ‰ł˛ ‡ ˇ `£ ˇ‚
—¡ø ¨ • †…¡£` ‰æˆ» —˚ Ø – ˆ —Ł „ ¨˝ —ˇ´ ‰˜
ˆ , ·¸ ´ ˚ˇ ˚– —§‚ —†»”‹ †¢†»» ¶¤…´ ¸ ¨˝
—ˇ´ ‰¡£
˛ ´ ˚ˇ ˚– —§‚ — “ ˜ ”ˇ ‰“ ¸ ¤ : N i¡¢
Mo¡¢Ti¡¢A l¨ , † —ˆ W ·œ Mo
[ 6 ]
, ˆ Cr·œ †¿ •
N i
[ 7·8 ]
, …˛ ”‹ ˝› ˜ ”ˇ ‰–¤ ,‚ˆ –¤ ¨ˇ ˛“ ˝› ¿
…¿ ˚– —§˙¿ »fl• ˜ ˛´ ¶¨ •¶ ˛§
[ 9 ]
¡£
˜ł ¿ Æ ‚ ´ ˚ˇ ˚– —§ ‚ »ø ˜ ¨˝ — , ˚˙ ˛“
¸ …¨¿ · ‰ł˛» · ˜ ‰»»‹ ˘ , —ß »æˆ ˝Œ¨« ˜
ı · ´ ˚ˇ ¡£´ ˚ˇ ˚– —§‚ —˜ł “ ¸ “ º ˙¿ »fl“ ¸ —˛
‡ ˙¿ »flˇ ˛ ‡ ,˚„ »ø —˜ N i”‹ `¿ ‰˝ ,¸ø ‚ —˜ł
”‹ `¿ †»˜ « ˝ ,¨ „ß˝ 10%˝ »Æ ˘ ¨˝ —ˇ´ ‰
[ 19 ]
¡£
˜ł ”‹ `¿ „ ¶ ,Æ ‚ `¸ „ ´ ˚ˇ ˜ ˛¨ ¶¤—,„ ¨ ” ¨·
˚– »Æ–£ ` ‰ˇ¶ ˜ †—` ´ ˚ˇ , ˚„ ˚– —§” ˜ ˙¿ ¶¨ ‰
˝
[ 20 ]
¡£ ·¸ ,“ –£⁄ ‚ `…”ˆ ˜ ˙¿ ¨˝ —,˜ł ¡¢ ¡¢ ¨ “
¸ ”‹ `¿ “ ¿ ˘ » ¶¤•¶ ˛§ ˜
[ 12 ]
¡£
˚˙ ˛ ´ ˚ˇ ˚– —§ ‚ — — —§ ˜ ˙¿ »fl “ ¸ ,¸
¿ º N i—˛‡ N i
3
( Ti, Mo) ,˚˙ ˛ ´ ˚ˇ ˚– —§‚ ˜
“ ˙¿ »flˇ ¡£ Tharian
[ 7 ]
¨ ¨ˇ ˛“ ,ˆ¿ … 01% (˚ `¿ •
˚ ,ˇ´ ˝‹ )˜ ,ƒ
02
… 54 MPa¡£ ”‹ `¿ † †»˜ „ ‚ ,
˛“ Ti¨ º —”ƒ“ ¸ —˛‡ ‚ —˛‹ ˜ …—˛ , ¨
º C—˛‡ ( Ti, Mo) C¿¯ `£ , ”˝ S¡¢O¡¢N ¨ —˛‡ Ti
2
S¡¢Ti
(C, N) ¡¢TiO
2
¨ …— ˛ , —'…—˛ »Æ †˜ `ˇ ˜ †¿—˛‡
˛¢ ¿ …` ˛˘ · ¶ł ˇ ˛£ ”ƒ‚ ˜ ¨˝ —¡£
º ”‹ ´ ˚ˇ ˚– —§‚ ˇ –¨ ,˛ ´ ˚ˇ ˚– —§‚ —
˛“ ˛ ‡ ˇ ˜ ˙¿ »fl ˆ …ı¨ı ,« ¿ Ł „ ˛ ‡ ˇ
§ ‰• †…,ˆ ‰ˇ‚ —¡ø ¨ ˙ ˆ ¢ • †…˜ ˛ ‡ ˇ ,· ¶ł ˘
‰–£‡ ‚ ˙¿ ¨˝ —˜ ˆ
[ 21 ]
¡£ ”‹ `¿ „ ‚ »Æ —˛ ‡ ‚
˛´ „ ¨ ·ƒ ˚– ¶… †» ¨ ‰ ˜ ‚» ‰ ˚ … »fl ”ˇ ˛ (¨
Fe
2
Mo) , ˘ ¨˝ —ˇ´ ‰¡£¨˛ »‡``
[ 9 ]
¨ˇ ˛“ , ”‹ ˝› ˛
´ ˚ˇ ˚– —§‚ — , ˜ ”‹ `¿ · 7%˚– ,‡ » ¨˝ —ˇ ł
ˇ´ ‰¡£
¶ ˆ ‚ı ·œ˜ł ˜ ˛ ‚
[ 6·7 ]
,˜ł ”˝ ‚ı ˜ ”‹ `¿ •¶ ˛§
“ ˇ ‚æ¿ ˘ ¡£“ ˆ ‰`…”ˆ ˜ ˙¿ ¨˝ —, (N i + Cr)˜ ”‹ `¿
ƒ ¿ ˘ 17% ¡« 2l%
[ 22 ]
¡£ A sayama
[ 7 ]
¨ˇ ˛“ ,˛ ´ ˚ˇ
˚– —§‚ —` —Ł“ ( 12¡« 14) %N i + 3% Cr, …ı
N i
3
Ti˛ ‡ ˘ »ø ˘¶ ˜ł ¶ł ‡ ˜ ¨˝ —¸ ˚§ , ¨
– ˜ 14N i·3Cr·3Mo·l5Ti‚ ˝ ˚˙ »ø ·¸ Ł …˘˜ ¡£
´` ˝¤ ‡£˚˙ ˛“ ˝ ı …`…¨º ‚ —˜ ,† ¿ ´ ˚ˇ
˚– —§‚ —†œœ † »fl , —ˆ ´` ˛“ ˛ ‚ ˙¿ »fl“ ¸
”˝ ˛ ”‹ ´` (1% ¡« 35% )´ ˚ˇ ˚– —§‚ ˜ –¤
[ 23·24 ]
¡£
„ ˇ¡ ˝` “ ¸ ¶ ˛ ´ ˚ˇ ˚– —§ ‚ — ˜ ˜ ˇ ˜
— ¿ »„ –¨ ‰ˇ ¡£ — ˚ `ˇ –¤ ,ˇ¡ ˝` “ ¸ ˜ Æ ‚ ´ ˚ˇ
˚– —§‚ ˜ ¸ ¨˝ —
[ 25 ]
¡£ ˛ „œ ˇ¡ ˝` ˚ · •Æ ‚» ,ƒ •‰
ˆ ‰ł——„ª •” ¶ł ¨º —¿ ¡£
3¡¡ ¨¨ ·ƒ ¶ ˛ ´ ˚ˇ ˚– —§‚ `ƒ § —
˜ ˜ ˇ
´ ˚ˇ ˚–—§ ‚ ˜ ¨¨ ·ƒ “ ˚˙ „ ¨ ”˝˚–—§ ,„ ¨
˛´ ¶¨ ˜ ‚ ˝ …¨ ˇ § `£ ˜ · —¡, ˇ ”ˇ ‰“ ¸ ˜ „
¨ ‡ ¶¨ , ” · ‡ ¶¨ ˇ ¶¤`¸ ˚– —§” ˜ —˜ ¡£˜¿ ˙ „
„ ¨ ˛´ ¶¨ ¶ ˛ ´ ˚ˇ ˚– —§‚ `ƒ § —˜ ˇ ˜ —¿
»„” ,† · » —'• ˘ ¡£
”˛ ª
[ 26 ]
¨ ¨¸ ¶ „œ ˜ —´ —˝ ˛ ´ ˚ˇ ˚– —§ ‚ ˜ —
¿ ¨ˇ ˛“ ,¡ „ „ ¨ ˛´ ¶¨ ( 800¡« 1200 ¡ )”˝ –£˛´ ˚– … ( 0
¡« 5 h)˜ – »fl•¶ ˛§ ¶…–¨ ‰ˇ· ,˘‰ø § `£ ‡ · · 20ƒ m
‡⁄ · ‰ 800 ƒ m, „ ¨ ‹ †˜ `ˇ ˜ † ¶¨ – »fl•¶ ˛§ ¨
8
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2 HRCfi …¡£¯ ˙¿
[ 14 ]
¶ „ ¨ ‹ T250˛ ‚ ˜ —˜ —
¿ – ˆ ,¸ ¯ „ ¨ ˛´ ¶¨ (800¡« 950 ¡ )”˝ –£˛´ ˚– … (1¡«
6 h)˜ – »fl ,† ¶¨ …‚”ı ˆ» —– »fl ( 280¡« 292 HB) ,¶ ˙
• ˙¿ ¶¨ ƒ
02
˜ ˇ † †» · (61 MPafi ˜ ) ¡£
Tharian
[ 8 ]
¶ ¡ ¶¨ ˛ ´ ˚ˇ ˚– —§ ‚ ‰ł ——`¸ — ¿ ,
¸ „ ¨ ˛´ ¶¨ (750¡« 950 ¡ )˜ Æ ‚ ,˚– —§‹ ˛ ´ ˚ˇ
˚– —§‚ ˜ ˙¿ ¶¨ · 1660 MPa»” ´ ‰˝ ‰ 1570 MPa,¶ł
´˚ · 6%ˇ ‰ 12%¡£”˛ ª
[ 26 ]
¨ ¨¸ ¨ˇ ˛“ ˚– —§ ‹
˛ ´ ˚ˇ ˚– —§ ‚ ˜ ˙ • ˙¿ ¶¨ ”˝ § `£ ‡ · fi … ” ”ˆ
•ß ”ˇ Hall·Petch„ ˇ ,¨ ˝… 1,¸ —¸ § `£ —‡ · ˜ ‡⁄
· ˆ» —ˆ ˇ – »fl ,– ˙¿ ¶¨ ‚ 1900 MPa˚– ,§ `£ ‰ł»
†‰‡⁄ · ¸ —»Æˇ ¶æ»fl¡£ ·¸ ¿ …ß,¶ ˜ —¿ ‰Æ„ß
—˙¿ ¶¨ º § `£ · —¡˜ „ ˇ ˚˙ » ´ ˜ ,¶ł ¸ —˜ – »fl„
´ ¨· —” · †»˝‹ , ˚˙ ˆ ¨º —¿ ˜ ¿˛ ¡£
˝…1¡¡ § `£ ‡ · ¶ ˛ ´ ˚ˇ ˚– —§‚ (00N i18Mo4Ti)
˙ • ˙¿ ¶¨ ˜ ˇ
[ 27 ]
Fig. 1¡¡ Effect of grain size on tensile strength of Co·free
maraging steel (00N i18Mo4Ti)
¨» ¶ł , Sinha
[ 27 ]
¨ ¶ 18N i˛ ´ ˚ˇ ˚– —§‚ ˜ —
¿ ¨ˇ ˛“ ,˛ ´ ˚˙ „ ¨ ‹ »„˚˙ ˚– —§‹ ˛ ´ ˚ˇ ˚– —§‚ ,
˘ › —˜ ¶…†»˚ § `£ ‡ · ˜ ˇ ¡£º ˙ ˜ ˚ Ø ‰Æ
„ß· ˇ ¶ ˝¥ ¡£
˚– —§·ƒ ¶ ˛ ´ ˚ˇ ˚– —§‚ `ƒ § —˜ ˜ ˇ †
—¨¸ `¸ » —'—¿
[ 28 ]
¡£ ˝… 2˚˙ †»˝‹ ˚– —§˛´ ¶¨ ˇ´ ,˚–
—§˚– …¶ T250˛ ´ ˚ˇ ˚– —§‚ † ¶¨ ˜ ˇ ¡£· ˝…
2—¿ ¿· ‡ , – ˚– —§˛´ ¶¨ ‰ˇ˝ ˚– ( 450 ¡ , 480 ¡ ) ,
T250‚ ˜ † ¶¨ ‚ ¸ ˇ ,” · – »fl¸ ¶¨ ˙ ˘‰»” ,†»
„ – ‰ 600 m in˚– † ¶¨ »„ —ˇ ˜ ˙ ˚˘ ; ‚ ˛´ ˚– —§·ƒ
˚– (550 ¡ , 600 ¡ ) ,† ¶¨ ¶…” ¿ · ‰• (• –
15 m in”˝ 5 m in) ,·¸ ” † ¶¨ ‰¥ˇ´ ‰¡£
¡¡ ¡¡ » ª · ¸ ,´ ˚ˇ ˚– —§‚ ˜ ˚– —§˛´ ¶¨ » ' ‡‹ „ ‚ˆ
‚ ˜ A s(´ ˚ˇ ˜ ˇ – )˛´ ¶¨ ,Ø fl —‰«»Æ‡ ˇ ˜ “ –
´ ˚ˇ ,»Æ˚„ ˙¿ ¶¨ ¡¢† ¶¨ ‰˝ ¡£ T250‚ ˜ A s˛´ ¶¨ ˚˙ ¶
‚ ,˝… 2— 550 ¡ ¡¢600 ¡ ˚– —§˙œˇ ˜ – »fl˚˙ ˙¿ »fl
ˇ ‡⁄ · ¸ø ´ ,»„˚˙ ˜ “ – ´ ˚ˇ ¸ø ´ ¶…—Ł“ ‰ł» †‰‰
¡£
˝…2¡¡ †»˝‹ ˜ ˚– —§˛´ ¶¨ ˇ´ ,˚– —§˚– …¶ T250˛ ´ ˚ˇ
˚– —§‚ † ¶¨ ˜ ˇ
[ 29 ]
Fig. 2¡¡ Effect of aging time on hardness of T250 Co·free
maraging steels at different temperatures
[ 29 ]
˛“ `¸ Æ ‚ ˛ ´ ˚ˇ ˚– —§ ‚ ˙¿ ¨˝ — ,»„ ¿ † ˆ
˘ ¸ß ˜ ¨¨ ·ƒ „⁄ ¡£ ¨ , ”‹ ‚ —† ˆ › »• ˇ –
„⁄ ,¿ ——§ ˇ‚ »fl§ `£ ,…«· Æ ‚ `¸ †˜ `ˇ ˜ ˙¿ ¨˝

[ 29·30 ]
¡£ „œ ˜ ˝ ˛ ‚ — ƒ ˆ ·¸ „⁄ ˜ –¤ »„ ”

[ 31 ]
¡£
4¡¡ ˛ ´ ˚ˇ ˚– —§‚ ˜ ˚– —§˙¿ »fl»œ
„ ¨ ‹ ´ ˚ˇ ˚–—§ ‚ ˜ ˙¿»fl “ · · „ ¨ ¡¢ ˛»
· … ˇ –˙¿»fl¨ ¡£” ¶ ˚ Ø–ˆ ´ ˚ˇ ı … »
ı ¿ ¶¨†»˚ § `£‡· ˜ ˇ
[ 28·29 ]
,˙ • ˙¿ ¶¨ º § `£ ‡
· ˜ ˛¢ ¨ı „ ˇ ,¿ ˜ ˚˙ § ‰˜ ˙¿ »fl ˆ –»
ı ‰˙¿ »fl¡¢„ ¨ ˙¿ »fl¡¢· `¿ ˜ ˛» · ˙¿ »fl¸ø ˝ ˆ» ‡ ˜ ¡£
˚– —§·ƒ ” ,§ `£ ‡ · –¨ ‰ˇ—¡˚– ,§ ‰ˆ » · ,˛ ‡ ˇ
†»»Æ § ‰†œœ · `¿ ˘« ;– § `£ ‡ · –¨ ‰ˇ· · ˚– ,˛
‡ ˇ »Æ § ‰¡¢ ı ‰·ƒ ˘« ,˚„ § `£ ˜ ˜ ˛ ‡ ˇ …ı
,· ¶ł ‡ `¸ ˙¿ ¶¨ ‰˝ ¡£§ ‰ˇ ‡` » ˇ ˆ ¶¨ ˜ …
»Æ—˛‡ – Ł › ˛» · ˜ »‹ ˘ ,˝‹ ˚– ‚ § `£ ˜ —› – —˛
˚ ‰ ˘ ,– ˇ ˛“ ¸ —‰˝ ¡£¶ł …—˛ »ø » § ‰
ˇ ˜ ˘« , »Æ—˛‡ ˛¢ ` ˛˘ » †œœ § ¶ˇ ` ,‰˝ †˜ `ˇ
˜ ¨˝ —
[ 29 ]
¡£ Sinha
[ 27 ]
¨ˇ ˛“ › — ˜ ”˝ § `£ ‡ · ˛ „ ¡¢
¨˝ — ¸ „ ¨ ˛´ ¶¨ ‚ ¶ł ¶æ »fl ,› ¿ ˜ ˚˙ ´ ˚ˇ
—˛ˆ† ¿Ø· “ – ‡ Ł ı · ‡ ˜ ¡£
˛ ´ ˚ˇ ˚– —§‚ •– ¶ ,˚– —§˛ ‡ ˇ † †»¡
ˇ ˝‹ ¡£ˇ —¿ ƒ ˆ ‰ˇ‡ ˚ ˜ ˚˙ C—˝”‹ ´ ˚ˇ ˚–
—§‚ ,¶ł T—˝˛ ´ ˚ˇ ˚– —§‚ ˜ —¿ »„–¨ ‰ˇ ¡£
Vanderwalker
[ 32 ]
¨ˇ ˛“ T250˛ ´ ˚ˇ ˚– —§‚ ˜
˚– —§˙¿ »flˇ ˚˙ N i
3
(Mo, Ti) ,˘ ˛ ‡ „ ‡ ˛“ : ˚ ˇ¨ ´
˚ˇ »ø ˜ •¢ œ N i˘« , N i˜ ˘« …´ ˜ – ´ ˚ˇ
˜ œ ‡ ,¸ ” N i
3
Ti ´ ˚ˇ ˜ —˛”¸ ¡¢‡⁄ · ,˘ ˛» ˇ …
—˛· ¨¡ ´ ˚ˇ ¡£ N i
3
Ti‡` ” ,†¿• ˜ – ´ ˚ˇ
– » ´ ˚ˇ ¡£˚– —§” ˘ †¿• Mo› ·œ `¸ Ti› —˛
‡ N i
3
(Mo, Ti) ¡£ Vasudevan
[ 15 ]
† ˆ • ˛ †¢ ‚¤ …˘
¸ª »œ ˜£ ˜ • ˛ ˘ ¶ C250”˝ T250‰ł——˜ —
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,˛ ´ ˚ˇ
˚– —§‚ ˚– —§˚– ˜ ˜ – ´ ˚ˇ † ¿ ‰ˇ˝ ˜ ˚– —§˛´
¶¨ ˇ´ —˛‡ ,» ¸ ‚ˆ ‚ ˜ A s˛´ ¶¨ ” ˝ , ˙ ˚˙ ¿ – ˜ ¡£
·
[ 33 ]
¨ˇ ˛“ ,”‹ ´ ˚ˇ ˚– —§‚ ˜ ˛ ‡ ·˛ —: ˚
ˇ¨ •¢ œ •ø • ‰,¨» ” N i·Mo·Ti‚» …fl˙ł › ˛» —˛”¸
•‰˚‰˛ ‡ ˙¿ »flˇ N i
3
(Mo, Ti) ,ˆ» —˜ – ´ ˚ˇ ˜ —…
„ ‡ ¡£‡ ˛‹
[ 16 ]
ˆ ‡¡ º ˇ ˛¢ › ‰ º •‰ •¤ ¶ T300
†»˝‹ ˚– —§˛´ ¶¨ ( 450 ¡« 610 ¡ ) ”˝ †»˝‹ ˚– —§˚– … ( 5
m in¡« 360 h)˜ ˛ ‡ ·˛ —‰ł——`¸ —¿ ,¨ˇ ˛“ ‚ˆ ‚ ˜ ˙¿ »fl
ˇ ˛“ N i
3
Ti”˝ Fe
7
Mo
6
, Fe
7
Mo
6
˚˙ ˚– —§ ” ˘ N i
3
Ti– ‰
ˇ —˛”¸ ¡¢‡⁄ · ,¶ł ˙ ˚– —§Ø fl —˛· •¢ ˇ ˜ – ´ ˚ˇ ¡£”˛
ª
[ 10 ]
¨ ¨¸ ¶ —´ —˝ ˛ ´ ˚ˇ ˚– —§ ‚ ˜ — ¿ ¨ˇ ˛“ :‚ˆ ‚
800 ¡ „ ¨ ¡¢480 ¡ ˚– —§12 h˜ ˛ ‡ ˇ ˛“ ˜ ˆ ‡ ¶¨ ˜
N i
3
( Ti,Mo) , « ˛· …˜ – ´ ˚ˇ ¡£¶ W250
[ 5 ]
˜ —
¿ – ˆ ,‚ˆ ‚ ˜ “ ˙¿ »flˇ ˚˙ ‰»‰Æ„„ ˜ N i
3
W ”˝
`ø •‰‰Æ„„ ˜ N i
3
Ti¡£„ ˚– —§·ƒ (650 ¡ ˚– —§3 h)” †¯
— 13% ( » • ˚ )˜ ˜ – ´ ˚ˇ ¡£˛˜ ˇ [ 15 ]¨ˇ ˛“ ,
˚– —§˙¿ »fl˜ ˚– —§‡ı ˘ , ˙¿ »fl—§„ß º ˛» · ˙—„ „† ‚æ˙ł
(‡` ˇ )¸ø “ ˙ ˜ ƒ `ƒ —„ ,·¸ ˚– „†‚æƒ `ƒ ”˝ ‡` ˇ
˜ †¿——»fl˘ “ ˆ ¡£¸ ¯ ‡` ˇ ˜ ‡⁄ · †¢º »ø
–£‡ º „†‚æ„ ˇ ,˛» · ˙—„ ¸ ˆ˙ ¸ø —Łƒ `ƒ †‰ …,˙
• ˙¿ ¶¨ ˇ ¡£‡` ˇ …—ł‡⁄ · ,‡ · · ‰» ¶¤ ˚– ,˛»
· » ˜ ¨˘ „ ¶ł ˛ •¤ ˙—„ ¡£—¶ —¿ ¶…– ˆ ˘ ˙¿ »fl»œ˘
¿ ˆ Orawan¨˘ „ »œ˘ · ‰˚˝
[ 10, 28 ]
¡£ ˛˜ ˇ [ 34 ]¨ˇ ˛“ ,
‡` ˇ ˜ ` ‰º ¶ ‡ · · ‰ 15–¶˜ Burgers˚‚ `¿ (…˛“
375 nm)˚– ,˛» · ˝ »Æ¨˘ „ ‡` ˇ ¡£– ‡` ˇ ˜ ¿¯ `£ …
· ‰˜‡ » ` ‰ ˚– ˙¿ ¶¨ · ‰• ¡£˛˜ ˇ [ 10 ]…˘¸ª ‡
˛ ´ ˚ˇ ˚– —§‚ • ˙¿ ¶¨ ˚– ‡` ˇ ˜ ` ‰¿¯ `£ …
˛“ 253 nm,‡` ˇ ˜ – ¶ ‡ · ˛“ 87 nm¡£
ˇ ¸ø ˚ ,„ ˛ ´ ˚ˇ ˚– —§‚ ˚– —§˙¿ »flˇ ˜
˛ ‡ ·˛ —¡¢˙¿ »flˇ ˜ —˝¡¢˚– —§„ ‡ —˜ – ´ ˚ˇ ˜ —˛
‡ ı …¡¢• †…¡¢˚ `¿ …˘ ¶ —˜ ˜ ˇ ¶…—Ł“ ‰ł——¨º
˜ —¿ ¡£
5¡¡ ‰Æ
˛“`¸ ˚„˛ ´ ˚ˇ ˚–—§ ‚ ˆ ‰„ª •”˜ ƒ ˆ , –
˚˙ – —˛`¿ ” · ˜ —„ –¡ – `ª …˜ œ †œ¡¢ƒ ˆ — ,ƒ
¨º —¿ ˘ „ ¨ ¡¢˚– —§„⁄ …˙¿ »fl»œ ;‰ł——˛ ´ ˚ˇ
˚– —§‚ › »• ˇ – ·ƒ „⁄ …˘ ˇ ¸ ˜ —¿ ,‰
¸ ‰ł» †‰Æ ‚ ˘ ˙¿ ¨˝ —˜ ˝ ¶ ; —¿ ˇ¡ ˝` “ ¸ ¶ ˛
´ ˚ˇ ˚– —§‚ ˜ ˆ …»œ ,˛“ ¿“ •¢ —˜ ‚ ”ˆ ˜ —´—˝
˛ ´ ˚ˇ ˚– —§‚ ¶¤ ´ »ø·¡ ¡£
†˛¿…˛˜ ˇ :
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[ A ]. W ilson R K. Maraging Steels Recent Developments and
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[ 14 ] ¡¡ ¯ ¡¡ ˙¿ ,˝ı ˆ …ł,¨ . „ ¨ ·ƒ ¶ T250˛ ´ ˚ˇ ˚– —§
‚ ˜ Ø fl …`ƒ § —˜ ˜ ˇ [ J ]. †˜ `ˇ ¨¨ ·ƒ § –¤ ,
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2007˜Œ¨« „œ˚§ —§• ˛ § ˚ı »ÆØ » ”¯ ˝¤ “
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»Æ „ª „†˝‹ ¿“ 2005˜Œ¨« „œ˚§ —§• ˛ § ˚ı »ÆØ fi
” ,`‰§ »Æ¶¤ 2007˜Œ 10´ ˇ fi » ·˛ ¨« „œ—
˚§ —§• ˛ ——· »Æ¡£»ÆØ ß ˙º ł ˆß ” ˚¿ ¡¢¤ …¨
ß –¤‚ , ‰Æ˚§ —§• ˛ º ⁄ • —¿ ‡ „ß ,‰»` › Ø ,‰
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1 1
¡¶‰ ˚ ¨¨ ·ƒ ¡•2007˜Œ 32 2˘
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20 5 ˘
2008 ˜Œ5 ´
¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡
¡¡ ¡¡ ¡¡ ¡¡ ‚ œ — ¿ § –¤
¡¡ ¡¡ ¡¡ Journal of Iron and Steel Research
Vol. 20 , No. 5
¡¡ May ¡¡ 2008
»ø‰ ˇ ˜¿ :„œ…‚ ……˚ı —¿ •¢ „ …˘»fi(863) ˚ œ ˇ ˜¿
…‰Ø:`ı æ –ƒ (19772) ,˜—,†' ˚¿ œ ; ¡¡ ¡¡ E2mail :liuzhenbao1977 @yahoo. com. cn ; ¡¡ ¡¡ —¶' ¨ ˘ :2007211220
—´ —˝ Cr2Co2Ni2Mo ˇ ´ ˚ˇ ˚– —§†»—‚ ˜ ˙¿ ¨˝ »fl»œ
`ı æ–ƒ, ¡¡ ´ , ¡¡ ” Æ“`œ , ¡¡ `” ‰£— , ¡¡ ¸ ˙ , ¡¡ ˛˜ » , ¡¡ ¸˛ ‡ˇ »
(‚ œ —¿ ” ‰Æ„„ ¸ø , ––' 100081)
“ ¡¡ “ :—¿ `¸ ˛ „œ ———˘ ˜ Cr2Ni2Co2Mo ˇ ‚ ˙¿ ¶¨ ´ ˚ˇ ˚– —§†»—‚ ˜ ˙¿ ¨˝ »fl»œ ¡£‰Æ„ß– ˆ ,‚ˆ ‚
535 ¡ ˚– —§˙¿ ¶¨ ¿ · 1 940 MPa , KIC = 141 MPa ¡⁄ m ,·¸ ˚– ‚ —˛ ‡ ˜ · `¿ ¡¢ˆ ¢ ¡¢ˇ‚ —¡˜ Fe2 Mo —˝Laves ˇ ˚˙
–£‡ ‡‹ ‚ ˙¿ ¶¨ ˜ “ › ; ˇ¸ ˇ‚ ˜ ´ ˚ˇ ı ‰ˇ — `¿ ˜ †— ´ ˚ˇ ˚„ ‚ —‰ˇ‚ ˜ ¨˝ —¡£‚ˆ ‚ —¯ `…
˜ ”ˇ —˜ , – ˚˚ ”ˇ ˘ —´» ·œ‚ ˙¿ ‚ ¨˝ ¡¢‡—`ƒ ˜ ˜˝ ”£ »• ‡ ‚fl ˚· ‰Æ„„ …,†¢ ”‰ …”‰¿ ` ˙– ¯ ƒ ˆ
˙ ¡£
„ …·˚ :´ ˚ˇ ˚– —§†»—‚ ;˙¿ ¨˝ »fl»œ ;˛ ‡ ˇ
—˝…• ”¯ : TG14211 ¡¡ ¡¡ ˛˜ ˇ –Œ˚¶ ´º :A ¡¡ ¡¡ ˛˜ ´ – ”¯ :100120963 (2008) 0520027206
Strengthening2Toughening Mechanism of an Cr2Co2Ni2Mo
Ultra2High Strength Maraging Stainless Steel
L IU Zhen2bao , ¡¡ YAN G Zhi2yong , ¡¡ YON G Qi2long , ¡¡L IAN GJian2xiong ,
SUN Yong2qing , ¡¡L I Wen2hui , ¡¡ SON G Cheng2yi
( Instit ute for St ruct ural Materials , Cent ral Iron and Steel Research Instit ute , Beijing 100081 , China)
Abstract :The strengthening2toughening mechanism of an domestic2produced Cr2Co2Ni2Mo ultra2high strength maraging
stainless steel was st udied. The result s show t hat after aging at 535 ¡ for 4 h t he st rengt h of t he steel may reach
1 940 MPa , and KIC can reach 141 MPa ¡⁄ m , large amount of precipitates are found in t he martensite , t he pre2
cipitates are very fine and dispersedly dist ributed in t he mat rix , which greatly enhances t he st rengt h of t he steel ,
and t he residual austenites between martensitic lat hs improve t he toughness of t he steel. The steel is especially sui2
ted to making a new generation of st ruct ural member wit h high st rengt h and high toughness , which can be used in
st rained marine environment , and it can be used in t he aerospace field.
Key words :maraging stainless steel ; st rengt hening2toughening mechanism;precipitation phase
¡¡ ¡¡ ´ ˚ˇ ˚– —§†» —‚ ˚˙ † ˆ ˝ … ´ ˚ˇ ˇ – ˙¿ »fl
”˝ ˚– —§˙¿ »fl—§ƒ …˜ ˚ ¶˛ ˚„ ‚ — ‚ ˜ ˙¿ ¨˝ —
”˝ ¯ ˜ ”ˇ —˜
[ 1¡« 4]
¡£ ‚ˆ ‚ ˚˙ – ˙ ¿„ › ˙¿ ¶¨ º ¨˝
— ˘¥ ¯ ”ˆ , ”ˇ —˜ …˜ ‰˚ ‰Æ„„ †˜ `ˇ ,„ª •” ƒ
ˆ ”‰¿ ¡¢”‰ ”˝ ”£ ¨ ‚ ¿˘ ……` , ‡ ˛“ ˆæˆ •
»œ¡¢‰¶• »œ¡¢‰¢ • »œ˘ ´ …¡¢˙– ˝§ ¶fl`ƒ ˆ ¨ ‡—`ƒ
˜˝ ˚· (» ‚ ˛´ ) †¿…˜ ˚ ¡ †˜ `ˇ
[ 5¡« 7 ]
¡£ ´ ˚ˇ ˚– —§ †»
— ‚ — ˜ ‚ ˙¿ ¡¢‚ ¨˝ ”˝ `… ”ˆ ˜ ˜˝ ˚· — ˜ ˚˙ ˘ ¸ ‚
†» ¿ ·œ ˜ ¡£ ‰ 40 ˜Œ˜ •¢ „ — ,‚ˆ ‚ ˛ ´ · ”ˇ
‰‡ • Ł …˘¡¢– `¶ „⁄ …˙¿ ¶¨ …¶– ø ˇ `¸ » ‚ —´
˜ ¸fi˘‰,¨ ˘ Æ ‚ ‚ ˜ ˙¿ ¶¨ •‰ˆ » – ˚˙ ‚ˆ ` —
¿ ˜ ¨¨ ª ¡£ · 1997 ˜Œ Martin
[ 8 ]
¨ Œ ˙º `¸ ´ ˚ˇ
˚– —§ †» — ‚ Custom465 ¤ ß (˘ ˙¿ ¶¨ ˛“ 1 800 MPa)
· ,´ ˚ˇ ˚– —§†»—‚ ˜ ˙¿ ¶¨ …¶– · 1 600 MPa
˝˘ ˇ `¸ ‚ ‚ ˜ ¸fi ˘‰, 2006 ˜Œ , ˆ „œ Ques Tek —´
……˚ı —ˇ ¨˛ „« ¸ ‡ „ƒ —˘ `¸ ´ ˚ˇ ˚– —§†»—‚
FerriumS53 , ˘ ˙¿ ¶¨ … ˛“ 1 980 MPa , KIC = 80
MPa ¡⁄ m ˇ
[ 9 ]
¡£
Menu
20 ˚ …˝70 ˜Œ·œ¿“ ˚…,„œ˜ ¿“ „ `¸ ´ ˚ˇ ˚– —§
†»—‚ ˜ —˘ „⁄ ,—˘ ˜ —˝‚ — 00Cr12Ni82
Cu2AlNb ,00Cr10Ni10Mo2 Ti1 ”˝ 00Cr13Ni8Mo22
NbTi
[ 10¡« 12]
¨ 10 ¡£2002¡« 2005 ˜Œ,‚ œ —¿ ”
‡ „ƒŁ …˘†¢—˘ ‡ —´—˝˜ ‡‹ ˝ …´ ˚ˇ ˚– —§†»—‚ ,
‚ˆ ‚ ˚˙ „œ˜ —•¢ †¢ — “ ˚¶ †œ¨¤ ˜ Cr2Ni2
Co2Mo ˇ ´ ˚ˇ ˚– —§†»—‚ ,˘ ˙¿ ¶¨ ˛“ 1 940 MPa ,
KIC = 141 MPa ¡⁄ m
[ 7 ,13 ]
¡£ ·¸ , –˚ ‰¸ ——¿
`¸ ‚ˆ ‚ ˜ ˙¿ ¨˝ »fl»œ , »fl`¸ ´ ˚ˇ ˚– —§†»—‚ ˜
˙¿ ¨˝ »fl ´ ¡£
1 ¡¡ ˚ Ø †˜ `ˇ ”˝ •‰•¤
¡¡ ¡¡˚ ؈ `ˇ †ˆ ¿ ‚—ƒ ´fl¨ `¶ ( VIM 3 t ) +
¿ ”˜ ´fl ¨ ˜ ¸« ¿ ¨ `¶ . ˚ Ø ‚ “ ‡ • ˛“ :
0102C2Fe213Cr24Ni213Co26Mo ¡£‚ ¶§› 1 150 ¡ …
¨¨ ”˝ ø ¨ »fl·ƒ ” ¶˝ ‡ <20 mm¡¢90 mm ¡` 90 mm ”˝
55 mm ¡` 55 mm ˜ †˜ , †¢…„⁄ ‡ ˚ ø ¡£ ˚ ø ›
1 050 ¡ ¡` 60 min „ ¨ ·ƒ + ¿ ( AC) ;‚” ˛´ ·ƒ
(‚ –øº ˘ « » ”ˇ ¨ ” ˛´ ¶¨ ¿ ˘ - 70 ¡ ) ;¨» ”
†»˝‹ ˛´ ¶¨ ( t = 440¡« 600 ¡ ) ˇ´ ˚– —§,–£˛´ 4 h¡£‡ »
˚ ø ”˝ › ˚ ø • – †˛ GB/ T22921994 ”˝ GB/
T22822002 –Œ… ,ˆ ˝‚ ( H2800) „ † ”˝ • ˛ `¸
‚ ˜ ˛¢ „ Ø fl ‰Æ„„ ¡£
2 ¡¡ ˚ Ø ‰Æ„ß
¡¡ ¡¡˝…1 ˛“ „ ¨ ”˝ ‚” ˛´ ·ƒ ” ˚– —§˛´ ¶¨ ¶ ˚ Ø ‚ `ƒ
§ —˜ ˜ ˇ ¡£¿ ¿· ‡ ,˚ Ø ‚ ˜ ˙¿ ¶¨ ( Rm , ReL
)
”˝ † ¶¨ ( HRC) ¸ ˚– —§˛´ ¶¨ ‚ ¶ł Æ ‚ , 535 ¡ ˚– —§
˚– ,‚ ˜ ˙¿ ¶¨ (1 940 MPa) ”˝ † ¶¨ ( HRC 54) ‡ ˇ `¸
˝…1 ¡¡ „ ¨ ”˝ ‚” ˛´ ·ƒ ” ˚– —§˛´ ¶¨ ¶ ˚ Ø ‚ `ƒ § —˜ ˜ ˇ
Fig11 ¡¡ Effects of aging temperature after solution and
subzero treatment on mechanical properties
• ,¸ ” ˙¿ ¶¨ ”˝ † ¶¨ ¸ ˚– —§˛´ ¶¨ ‚ ¶ł ‰˝ ¡£‡
» „ƒ ( A KU2 ˛“ ¶¨ 2 mm ˜ U —˝¨– ¿ ˚ ø ˜ ‡ » „ƒ)
¸ ˚– —§˛´ ¶¨ ‚ ‰¥ˇ´ ‰‰ ˝ ª (535 ¡ ˚– ) ,¨»
” ˇ [ ˝…1 (a ¡¢b) ] ¡£ · ¿· ,¶ˇ ˆ ˚ ¸ı ´˚ ( Z)
”˝ ‡⁄ ´˚ ( A) ˜ – »fl†»ˆ ˇ (¨ ˘ ˚˙ ” ) ¡£« ˚– —§
˛´ ¶¨ 440¡« 480 ¡ ˚– ,¶ˇ ˆ ˚ ¸ı ´˚ ‡˚ ˇ ‡ »”´ ˇ´ ‰
˜ ˙ ˚˘ , 480 ¡ ‡ ˇ `¸ » ‚ ‰ˇ˝ ,¸ ¯ ˚– —§˛´ ¶¨
˜ ‚ ,¶ˇ ˆ ˚ ¸ı ´˚ ”˝ ‡⁄ ´˚ »”´ ˇ ,¶ł 535 ¡
˚– ¶ˇ ˆ ˚ ¸ı ´˚ ¿“ ˚…ˇ´ ‰[ ˝…1 (c) ] ¡£
3 ¡¡ ˙¿ ¨˝ »fl»œ
311 ¡¡ ‡‹ ˇ‚ ´ ˚ˇ ı
¡¡ ¡¡ ˝…2 ˚ ‡ `¸ „ ¨ ·ƒ + ‚” ˛´ ·ƒ + 535 ¡ ¡` 4 h
˚– —§·ƒ ” ˚ Ø ‚ ˜ TEM Ø fl … ı ¿ ¶¨ ˜ •
¯ ¡£· ˝…2 (a ,b) ¿ …ß,Ø fl “ ˚˙ ˇ‚ —¡˜ ı ´ ˚ˇ
(M) ¡£· ˝…2 (c) —´ ˚ˇ ı ˜ ‡ · ¿ …ß,¿ ¶¨
—¡ 200 nm ˜ ´ ˚ˇ ı …… 70 % ,˘‰ø ı ¿
¶¨ …˛“ 197 nm ,ˇ¸ ˇ‚ · ı ´ ˚ˇ –£⁄ ‚ —‰ˇ
‚ ˙¿ ¶¨ ˜ ˝‹ ˚– »„ —`…”ˆ ˜ ¨˝ —¡£˝…2 ( b) ˇ ˚ ‡
ˇ‚ —¡´ ˚ˇ · ( MT
) ˙—‚ ´ ˚ˇ ı ˜ « ˇ‚ ‰Æ„„ ¡£
¿ …ß´ ˚ˇ ı –»¶ ‚ ‰˙¶¨ ¯¯ `—¡¢º ı ‡⁄ Æ ‡˚ ‰
60¡ª˜ —¡´ ˚ˇ · ˙—‚ ‡ ¶ ¶˛ ¶ł ¸Ø»fl¡£ †˜ `ˇ ˙¿ ¶¨
§ — ,ˇ‚ »fl§ `£ ˜ ˙¿ ¨˝ »fl—§„ß ˝¤ ‡£ˆ Hall2Petch „«
˚‰· ˆŁ˚ ,…·:
¡¡ ¡¡ Re = Re0 + ky d
- 1/ 2
(1)
˚‰— , Re0 ˛“ › ˚… ˙ • ˙¿ ¶¨ ; ky ˛“ ‡£ ˚ ; d ˛“¡ — —§§
`£ ¡–‡ · ¡£
¡¡ ¡¡Nalyer ‰«˚‰(1) — ˛“ Re = Re0 + ky D
- 1
M ¡£ ·¸ ˚‰
–» „ª •” ƒ ˆ ,˚‰— D
- 1
M ˛“ ´ ˚ˇ ı ˚ł – ¶ , ¸ º
ı ˜ „ ˇ ˛“ :
¡¡ ¡¡ DM =
2
ƒ—
{Wl n t g
arccos
W
L
2
+
ƒ—
4
+
ƒ—
2
L - Larccos
W
L
} (2)
˚‰— ,W ˛“ ı ¿ ¶¨ ; L ˛“ ı ‡⁄ ¶¨ ¡£
¡¡ ¡¡ ˚‰(1) ¿ “ ,ˇ¸ ˇ‚ ˜ ı ‡ · (» ——§§ `£ ) ”˝
´ ˚ˇ ı ¿ ¶¨ ˜ ˇ‚ »fl…‡⁄ ¶¨ •‰ˇ ˜ ˇ‚ »fl[ ˝…2(b) ] ,
…¨˚˙ Æ‚ ˙¿ ¶¨ , ˚˙ …¨˝ —˜ “ ¸
[ 14]
¡£
312 ¡¡ ˜ ˆ …¶˛ ‡ ˇ
¡¡ ¡¡ › 535 ¡ ¡`4 h ˚– —§·ƒ ” , ı ´ ˚ˇ ˇ ˛
‡ `¸ · `¿ ˜ ¡¢ˆ ¢ ˜ ˜ ˆ …¶˙¿ »flˇ ¡£– 1 `—‡ `¸ †»˝‹
˚–—§ ˛´ ¶¨ ·ƒ ” ˛ ‡ ˇ ˜ ‡ · • †…¡£¿ ¿· ‡ ,535 ¡ ¡`
¡⁄ 8 2 ¡⁄ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ‚ ¡¡ œ ¡¡ — ¡¡ ¿ ¡¡ § ¡¡ –¤ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ 20
Menu
2 ¡¡ ı ´ ˚ˇ —˛ˆ† ”˝ ‡ ·
Fig12 ¡¡ Size and shape of martensite lath
– 1 ¡¡ ˛ ‡ ˇ ‡ · • †…
Table 1 ¡¡ Size of precipitation phase
˚–—§ ·ƒ ˘ ¶¨ – ¶ / nm » –¨ / %
535 ¡ ¡` 4 h 5¡« 10 85
10¡« 20 10
> 10 5
600 ¡ ¡` 4 h 5¡« 10 20
10¡« 50 50
> 50 30
4 h ˚– —§·ƒ ” ‚ —— 85 %˜ ˛ ‡ ˇ ‡ · —¡ 10
nm¡£ —'˛ ‡ ˇ ¶⁄ œ ˛» · ”˝ ´ ˚ˇ ı ‰ˇ ,Ł
› `¸ ˛» · ˜ ˘ ¶fl , · · Æ ‚ `¸ ‚ ˜ ˙¿ ¶¨ , ¨ ˝…1 —
535 ¡ ¡` 4 h ˚– —§·ƒ ” ,‚ ˜ ˙¿ ¶¨ · ‰• ¡£
¡¡ ¡¡ † ˆ H800 ˝‚ „ † `¸ 535 ¡ ¡`4 h ,600 ¡ ¡`
4 h ˚– —§·ƒ ” ˚ Ø ‚ ˜ ˛¢ „ Ø fl ,‰Æ„ß˚ ˝…3¡«
5 ¡£¿ …ß,‚ — “ ˛ ‡ ˇ ˛“ `ø •‰‰Æ„„ ( TCP ˝ ˘¸ ˆ
¯¯ ‰Æ„„ ) Fe2 Mo —˝˜ Laves ˇ ( a = 01474 nm , c =
01772 nm) ¡£ ˚ Ø ‚ ˛“ ˝ …´ ˚ˇ ˚– —§†»—‚ ,
˚– —§„ ‡ —…»fl˛ ˛ ‡ `¿ ” ,¶ł ˙ † ˛· „ † ‰
…»fl˛ ¡£ ˛ ‡ ˇ ˜ SAD ˝……–Œ¶¤¿ “ : (110)
M ¡˛
(212)
L3 , ( 110)
M ¡˛ ( 212)
L1 ¡˛ ( 212)
L2 ¡˛ ( 212)
L3 ,
[ 115 ]M ¡˛ [ 162 ]L1 ¡˛ [ 261 ]L2 ¡˛ [ 467 ]L3 ,¶ł ˙ ¿ ¿· ‡ ,
˚ł ´ ˚ˇ [ 115 ]M •‰ ˇ ¨º ,Laves ˇ ‡˚ † ˙
· ¡£
¡¡ ¡¡ ˝…4 ˛“ ˚ł ´ ˚ˇ [ 112 ]M •‰ ˇ ¨º ˆ ‰
˜ 535 ¡ ¡` 4 h ˚– —§·ƒ ” ˚ Ø ‚ ˛ ‡ ˇ ˜ ˛¢ „ Ø
fl ¡£ ˝…4 (a ,b) ¿ “ ,˛ ‡ ˇ ˇ‚ —¡¡¢ˆ ¢ , ¸ ˆ˙
fi …˜ ˛» ˇ „ ˇ †»˝‹ ,„˚ ˛ ‡ ˇ ˜ ‡˜ ¶¨ …·ˆ ‡ ¶¨ †
†»˝‹ ¡£˝…4 (c , d) –Œ¶¤‰Æ„ß– ˆ : [ 112 ]M ¡˛ [ 592 ]L1 ¡˛
[ 354 ]L2 ¡˛ [ 331 ]L3 , ( 110)
M ¡˛ ( 112)
L1 ¡˛ ( 112)
L2 ¡˛
(103)
L3 ¡£ ˛ ‡ ˇ º »ø –£ ‡ `… ”ˆ ˜ „† ‚æ „ ˇ ,†¢˙
ł · ¶ ˚ ˛ ‡ ˇ ˛» · ˇ ‚‰‰œ ‡ ,¸ ˆ˙ Ł › ˛» ·
˜ ¸ ¶fl ,˚˙ · •ø ¶¨ Æ‚ ‚ ˜ ˙¿ ¶¨ ˜ “ ¸ ¡£
¡¡ ¡¡ ˝…5 ˛“ 600 ¡ ¡` 4 h ˚– —§·ƒ ” ˚ Ø ‚ ˜ TEM
Ø fl ¡¢SAD ˝……˘ –Œ¶¤ ¡£¿ ¿· ‡ , ¸ ˚– —§˛´ ¶¨
‚ ,Laves ˇ ˆ ˇ …fl‡⁄ · , ˚ł [ 112 ]M •‰ ˇ ¨º
ˆ ‰ ˘ ª › –Œ ¶¤ ” ¿ “ : [112]M ¡˛ [ 185]L1 ¡˛
[ 232 ]L2 ¡˛ [ 234 ]L3 ¡˛ [ 122 ]L4 , ( 110)
M ¡˛ ( 212)
L1 ¡˛
(122)
L2 ¡˛ ( 122)
L3 ¡˛ ( 212)
L4 , ( 110)
M ¡˛ ( 122)
L3 ¡˛
(212)
L4 ¡£ ˛ ‡ ˇ ˜ ‡⁄ · ˚„ ˛ ‡ ˇ ˜ ˆ ¢ ˙¿ »fl
—§ „ß ˇ´ ‰ ,· ¶ł ´ ˚„ ‚ ˜ ˙¿ ¶¨ ‰˝ ¡£
¡¡ ¡¡ æ ¨
[ 15 ]
— ¿ 0110C214Cr212Co2415Mo
‚ ˚– † •¢ ˇ `¸ Fe2 Mo —˝Laves ˇ ,†¢ˆ ‰‡ ‚ˆ ˇ º
´ ˚ˇ § § ˜ „ ˇ , …·: [ 2 1 10 ] ¡˛ [ 1 11 ]M ,
(0001)
L ¡˛ ( 112)
M ¡£ K. J . Irvine
[ 16]
¨ — ¿ `¸ 12Cr2
8Mo215Co ‚ 600 ¡ ˇ » » ˚– Laves ˇ ˜ ˛ ‡ ;
Kasak
[ 17¡« 19]
¨ •¢ ˇ AFC277 ‚ ˛´ ¶¨ ‚ 650 ¡ »
» ˚– ,— Laves ˇ ‡` ,†¢˝˘ ¶ˇ º ‚ˆ ‚ 565 ¡ » » ˚–
‡ ˇ ˜ † »fl• —ˇ „ ,« †¢˛· ¨• ¶¤˘ ˙¿ »fl ˆ ¡£–
˚ Ø ‰Æ”ˇ ˙ ¨¸ ¸ø ˆ ‰Æ´ ,†¢ ‡‹ ˝ … Co2Cr2Mo2Ni
ˇ ´ ˚ˇ ˚– —§†»—‚ —„ † ‰`¸ Laves ˇ ,†¢⁄ ˆ
Laves ˇ ¶ ‚ —” ˙¿ ˜ † »fl—§„ß ¡£
313 ¡¡ †— ´ ˚ˇ ˜ ¨˝ »fl ˆ
¡¡ ¡¡ ˝‚ „ † ‰Æ„ß– ˆ ,› 1 050 ¡ „ ¨ ·ƒ
” ,†»˝‹ ˚– —§·ƒ ˜ »ø Ø fl ˛“ ´ ˚ˇ + †— ´ ˚ˇ
¡£˝…6 ˛“ 535 ¡ ¡` 4 h ˚– —§·ƒ ” ˚ Ø ‚ ˜ ˝‚
˘‹ ¡£¿ …ß,†— ´ ˚ˇ ı ´ ˚ˇ ˚ł fi …
» ˘‹ · ´ ˚ˇ ˛§ ‡˚ –¡ ˘‹ · • †…, ¶ ‚˜ ˘ †˜ `ˇ ˜
¨˝ —˚fi• —ß ,†»‰¿ Ł „ ` ˛˘ ´ ˚ˇ ı …˜
' „ ,»„¿ …ı»” ı …ˆ …fl¯¯ `—˚– ˛» · ˙ ¶¸ ˘
˜ ƒ `ƒ …fl— ¡£ –Œ¶¤‰Æ„ß ¿ “ ,†— ´ ˚ˇ º ´ ˚ˇ
–£‡ `…”ˆ ˜ K2S „ ˇ ¡£ G. Thomas
[ 20]
¶ Fe2Cr2C
ˇ ´ ˚ˇ ‚ —¿ —† „ † ‰¶ˇ ` ¨˝ —º †— ´ ˚ˇ
¡⁄ 9 2 ¡⁄ 5 ˘ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ `ı æ –ƒ¨ :—´—˝Cr2Co2Ni2Mo ˇ ´ ˚ˇ ˚– —§†»—‚ ˜ ˙¿ ¨˝ »fl»œ ¡¡ ¡¡
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0 3 ¡⁄ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ‚ ¡¡ œ ¡¡ — ¡¡ ¿ ¡¡ § ¡¡ –¤ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ 20
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1 3 ¡⁄ 5 ˘ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ `ı æ –ƒ¨ :—´—˝Cr2Co2Ni2Mo ˇ ´ ˚ˇ ˚– —§†»—‚ ˜ ˙¿ ¨˝ »fl»œ ¡¡ ¡¡
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,¨ˇ ˛“ ˛¨ ¶¤˜ †— ´ ˚ˇ –¡ ˜⁄ · ı ´
˚ˇ fi …¶ ¨˝ ——ß ¡£
4 ¡¡ ´
¡¡ ¡¡ – —¿ ˜ Cr2Ni2Co2Mo ˇ ‚ ˙¿ ¶¨ ´ ˚ˇ ˚–
—§†»—‚ ‡ • •¶ ˛§ ˜ ,˙¿ ¨˝ »fl»œ “ ¤ :‚ ˛» ·
ˆ ¶¨ ˇ¸ ˇ‚ ı ´ ˚ˇ ˙¿ »fl…¨˝ »fl ˆ ”˝ ‡‹ ˇ‚ ı ˜
¶ ·˛ ˇ‚ »fl¡ ——§§ `£ ¡– ˆ ;‡` ˛ ‡ Laves ˇ ˜ ˆ
¢ ˙¿ »fl ;†— ´ ˚ˇ –¡ ˜⁄ • †… ı ‰ˇ ,†¢º ˘ –£
‡ `…”ˆ ˜ K2S „ ˇ ø ¶ ‚ ˘ ‰¨˝ »fl˜ ˆ ¡£˝¤ „
„ † Laves ˇ …†»˝‹ ˛» ˇ ‰Æ„ß•¢ ˇ ,Laves ˇ º
´ ˚ˇ »ø ˜ § § „ ˇ ˛“ : [ 21 10 ]L ¡˛ [ 1 10 ]M ,
(0001)
L ¡˛ (110)
M ,†¢˙ ´ ˚ˇ ˜ [ 1 10 ]M •‰ ˇ ˜
‡⁄ · ¸ ¶¨ ‰ˇ ¿ ¡£
5 ¡¡ ‰Æ´
¡¡ ¡¡(1) ˚ Ø ¸ø —¿ ˜ Cr2Ni2Co2Mo ˇ ‚ ˙¿ ¶¨ ´ ˚ˇ
˚– —§†»—‚ ‡ • •¶ ˛§ ˜ ,› „ 1 050 ¡ ¡` 1 h (AC) +
- 73 ¡ ¡` 8 h + 535 ¡ ¡` 4 h ( AC) ·ƒ ” ,‚ ˜ ˙¿ ¶¨
¿ · 1 940 MPa , KIC = 141 MPa ¡⁄ m¡£
¡¡ ¡¡ (2) ˚– —§·ƒ ” ,˚ Ø ‚ ˜ ˛¢ „ Ø fl ˛“ ˇ¸ ˇ‚ ˜
ı ´ ˚ˇ + `¿ ˜ †— ´ ˚ˇ ¡£ˇ¸ ˇ‚ ˜ ´ ˚ˇ Ø fl
˚„ ‚ —‰ˇ‚ ˙¿ ¶¨ ˜ ˝‹ ˚– »„ —`…”ˆ ˜ ¨˝ —¡£
¡¡ ¡¡ (3) › 535 ¡ ¡` 4 h ˚– —§·ƒ ” ,˚ Ø ‚ —˛ ‡
`¸ · `¿ ¡¢ˆ ¢ ¡¢ˇ‚ —¡˜ Fe2 Mo —˝Laves ˇ ,¸ ˆ˙ • †…
´ ˚ˇ ı ˇ ,†¢º »ø –£‡ `…”ˆ ˜ „†‚æ„ ˇ ¡£
—'˛ ‡ ˇ ¶⁄ œ ˛» · ˇ ‚‰‰,ˇ ł Æ‚ `¸ ‚ ˜ ˙¿ ¶¨ ¡£
Laves ˇ º ´ ˚ˇ fi …˜ § § „ ˇ ˛“ : [ 21 10 ]L ¡˛
[ 1 10 ]M , (0001)
L ¡˛ (110)
M ¡£
¡¡ ¡¡ (4) †— ´ ˚ˇ º ´ ˚ˇ –£‡ ¯ K2S „ ˇ ,†—
´ ˚ˇ ı ´ ˚ˇ ˚ł fi …» ˘‹ · ´ ˚ˇ ˛§ ‡˚
–¡ ˘‹ · • †…,¶ ‚˜ ˘ †˜ `ˇ ˜ ¨˝ —˚fi• —ß ¡£
†˛¿…˛˜ ˇ :
[ 1] ¡¡ Crawfird W M , Cont ractor G P. The Effect s of St rengt hening
Be and Ti in Maraging Stainless Steel [J ] . J IPI ,1969 ,207
(12) :1642.
[ 2] ¡¡ ˛” æ . ´ ˚ˇ ˚– —§†»—‚ [J ] . —´‰˚ †˜ `ˇ ,1972 , (4) :22.
[ 3] ¡¡ Imrie W H. Maraging Steel in t he British Aerospace Indust ry
[J ] . Metal Forming ,1970 , (1 ,2) :41.
[ 4] ¡¡ ‰“¡¡ ‰ , · , ·¤ , ¨ . ´ ˚ˇ ˚– —§†»—‚ ˜ •¢ „ ˇ ·
[J ] . ˚ ‚ ,2003 ,24(3) :1.
[ 5] ¡¡ Wil son R K. Maraging Steel s2Recent Development and Appli2
cations [J ] . Tmsaime Warrendale PA ,1988 ,1 :255.
[ 6] ¡¡ ˇ¨ · , »˘ „ »˝ . „œ˝ †»—‚ ˇ · …¶flˇ [J ] . „œ˝ ‰˚ †˜ `ˇ ,
1980 , (5) :1.
[ 7] ¡¡ `ı æ –ƒ , ¸˛ ˛“ ¸‡ , ´ , ¨ . ˚– —§¶ ‡‹ ‚ ˙¿ ´ ˚ˇ ˚– —§†»—
‚ Ø fl º —˜ ˜ ˇ [J ] . †˜ `ˇ ¨¨ ·ƒ § –¤ ,2005 ,26 (4) :52.
[ 8] ¡¡ Martin. U. S , Patent s 5 ,681 ,528.
[ 9] ¡¡ Charles J , Kuehmann Ph D. Comput ational Design of High2
St rengt h : High2Toughness Stainless Steel for Carrier2Based
Aircraft [ EB/ OL] . (2005211210) [ 2007211220] . http :/ / www.
morisan. com/ ferriums53. pdf .
[ 10] ¡¡ ´‰˚ ¢ , ¯ ˝¢ ¿› . †»—‚ [ M] . ––' : › ˜ ‡ ,1995.
[ 11] ¡¡ ¸˛ ˛“ ¸‡ , ˇ¨ · . ˛ „œ‚ ˙¿ ¶¨ †»—‚ ˜ •¢ „ ˇ · ”˝ „ ˝ß [J ] .
†»—,2000 ,4(2) :1.
[ 12] ¡¡ ´‰˚ ¢ . ˛ „œ†»—‚ —¿ º ƒ ˆ ˜ » „¸ ”˝ ‰ł†‰•¢ „ ˜ „ ˝ß
[J ] . ‚ œ —¿ § –¤ ,1966 ,8 (2) :64.
[ 13] ¡¡ `ı æ –ƒ , ´ . „ ¨ ·ƒ ¶ —´—˝´ ˚ˇ ˚– —§†»—‚ `ƒ § —
˜ ˇ —¿ [J ] . ‚ œ ,2007 ,42(3) :47.
[ 14] ¡¡ æ , ·” , ¡¡ , ¨ . » ‡‹ ‚ ˙¿ ¶¨ †»—‚ ˇ‚ »flØ
fl TEM —¿ [J ] . ”‰¿ †˜ `ˇ § –¤ ,2005 ,25 (2) :1.
[ 15] ¡¡ æ , ·” , ¡¡ , ¨ . » ‚ ˙¿ ¶¨ †»—‚ ‡ ´ ‚ ˙¿
»flˇ —¿ [J ] . ”‰¿ †˜ `ˇ § –¤ ,2003 ,23(1) :1.
[ 16] ¡¡ Irvine KJ . The Development of High St rengt h Steel [J ] . J of
t he Iron and Steel Inst ,1962 ,200(10) :820.
[ 17] ¡¡ Kasak A , Chandhok C k , Dulis E J . Development of Precipi2
tation Hardening Cr2Mo2Co Stainless Steel [J ] . Trans ASM ,
1963 ,56 :455.
[ 18] ¡¡ Versnyder F L , Beat tle J R H J . The Laves and Chiphases in
aModified 12Cr Stainless Alloy [J ] . Trans of ASM ,1955 ,47 :
211.
[ 19] ¡¡ Kout sky J , J ezek. Composition of Precipitates in Modified
12 % Chromium Steel s in t he Range Above 550 ¡ [J ] . Jour2
nal of t he Iron and St eel Inst ,1962 ,11 :938.
[ 20] ¡¡ Thomas G. Retained Austenit e and Tempered Martensite
Embrit tlement [J ] . Met all Trans ,1978 ,9A(3) :439.
¡⁄ 2 3 ¡⁄ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ‚ ¡¡ œ ¡¡ — ¡¡ ¿ ¡¡ § ¡¡ –¤ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ ¡¡ 20
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43 ¡¡ 4 ˘
¡¡ 2 0 0 8 ˜Œ 4 ´
‚ œ
Iron and Steel
¡¡ Vol. 43 , No. 4
April ¡¡ 2008
⁄ ˇ¨ – —˛ ¶ ´ ˚ˇ ˚– —§ ‚ ˙¿ »fl ˜ ˇ
¿ ‰ , ¡¡ ¸ ¡¡ ‰ , ¡¡ ‡´ …˛
(—„œ‚ —¿˘ ………fl˝¯ „«¸ , ––' ¡¡ 100081)
“ ¡¡ “ : ˇ ˝‡ —¿ `¸ ⁄ ˇ¨ – —˛¶ ´ ˚ˇ ˚– —§‚ ˙¿ »fl˜ ˇ ,—¿ ‰Æ„ß– ˆ :510 ¡ ¡` 3 h ˚– —§ ˘ ˜ ˙¿ ¶¨ »
… ”ª ¶¤ ,º – —˛`¿ ˛ „ , ˜ ˙¿ ¶¨ ˛“ :ƒ =ƒ
0 +ƒ⁄ƒ
CR +ƒ⁄ƒ
Age ,…·‡ı ˚…˙¿ ¶¨ ¡¢ …„⁄ ˙¿ »fl”˝ ˚– —§˙¿ »fl˜ … ,˘
—» — …„⁄ ˙¿ »flƒ⁄ƒ
CR¸ – —˛ `¿ – »fl ¡£ »¤ ø … ˙¿ ¶¨ • †… ⁄ ˚ :510 ¡ ¡` 3 h ˚– —§” ´ ˚ˇ »ø ˜
˛ ‡ `ø •‰‰Æ„„ ˜ Ni3
( Ti ,Mo) ”˝ ‰»‰Æ„„ ˜ Ni3 Mo , – —˛`¿ ¶ ˚– —§˛ ‡ ——˛“ ˆ» —ˆ ˇ ˜ ˇ ¡£
„ …·˚ : ´ ˚ˇ ˚– —§‚ ; – —˛; ˚– —§; ˙¿ »fl
—˝…• ”¯ : TG142. 7 ¡¡ ¡¡ ˛˜ ˇ –Œ˚¶ ´º : A ¡¡ ¡¡ ˛˜ ´ – ”¯ : 04492749X(2008) 0420066204
Effect of Prior Cold Roll ing Def ormation on
Strengthening of Maraging Steel
YAN G Zhuo2yue , ¡¡ SU Jie , ¡¡ CHEN Jia2yan
(China Iron and Steel Research Instit ute Group , Beijing 100081 , China)
Abstract : The effect of cold rolling deformation prior to aging on t he st rengt hening of a maraging steel was investi2
gated. The result s of experiment s indicated t hat t he net st rengt h increment caused by aging at 510 ¡ for 3 h is al2
most constant , irrespective of percentage of reduction in t hickness. Final st rengt h can be expressed asƒ =ƒ
0 +ƒ⁄ƒ
CR
+ƒ⁄ƒ
Age ,whereƒ
0 is initial st rengt h , andƒ⁄ƒ
CR andƒ⁄ƒ
Age are st rengt hening cont ribution due to cold working and aging
respectively , andƒ⁄ƒ
CR is only related to percentage of reduction in t hickness. It was confirmed by elect ron diff raction
analysis t hat t he st rengt hening precipitates are Ni3
( Ti , Mo) and Ni3 Mo , regardless of percentage of reduction in
t hickness.
Key words : maraging steel ; cold rolling ; ageing ; st rengt hening
… ‰Ø: ¿ ‰ (19622) , ˜— ; ¡¡ ¡¡ E2mail : yangzhuoyue @nercast . com; ¡¡ ¡¡ —¶' ¨ ˘ : 2007210212
¡¡ ¡¡ ´ ˚ˇ ˚– —§‚ ˝¤ „ ˚– —§˛ ‡ ‰ ˚ … »fl ”ˇ ˛ »æ ˆ
‡‹ ‚ ˙¿ ¶¨ ,˝‹ ˚– —ª „»˜ ¨˝ —”˝ ¸ —,› „ ‰ 50
˜Œ˜ —¿ ”˝ ƒ ˆ ,´ ˚ˇ ˚– —§‚ ˜ ˛ – ‰…˘ ¡¢
…„⁄ „⁄ ¨ ˙ ‡ ˚ ,ƒ ˆ ` ¨ ˝ ¿ ¡£` » •‰
ˆ ,‡‹ ˝ …´ ˚ˇ ˚– —§‚ „ ¨ ·ƒ (·ª » ) —˛‡ ˜ ´
˚ˇ ˇ ¶ ‰ˇ¨ ,¨˝ —”˝ ¸ —” ”ˆ ,¿ …„⁄ ‡ ‚
—˝†˜ ,´œª ‚ —˜ “ ˙
[ 1¡« 4 ]
,˘ —˚– —§˙ – —˛
†»‰Æ‚ ˙¿ ¶¨ ,¶ł ˙ ¿ ‚˜ ˘ ·¯ —, ˛“ ·¯ —”ˇ ‰ƒ
ˆ ·¯ ˝ »œ“ ¨ ‰Æ„„ ˇ
[ 3 ,4 ]
¡£ » —' — ¿ – ˆ :
‡‹ ˝ …´ ˚ˇ ˚– —§‚ …„⁄ † »fl‚ ˚ ‰ˇ˝ ,˚– —§
˙ – —˛˙¿ »fl—ˇ ,¨ 18Ni (350) ´ ˚ˇ ˚– —§‚
„ ¨ ” – —˛25 %¡¢510 ¡ ¡` 3 h ˚– —§” ˙¿ ¶¨ ‰
–¨ ˛· – —˛˜ †˜ `ˇ Æ ‚ 0. 5 %
[ 1 ]
, Kula ¶ 18Ni (250)
´ ˚ˇ ˚– —§‚ † ˆ ‰ ¸˘ ‰Æ„ß ¡£ « Lee ¶ 18Ni
(250) ´ ˚ˇ ˚– —§‚ „ ˜ —¿ – ˆ : ” – ‰
˚– —§–¨ —´„ ¨ ” ˚– —§˜ †˜ `ˇ ˙¿ ¶¨ ‚ ‡ 17 %
ˇ
[ 5 ]
¡£ – ˛˜ ˇ ˝‡ — ¿ `¸ 18Ni ´ ˚ˇ ˚– —§‚ –
—˛˜ ˙¿ »fl , –ª ‡˛ ˙ ˇ ˚ ø Ø ,†¢˛“ ¯ »fl ˘ „⁄
Æ„' ¡£
1 ¡¡ ˚ Ø †˜ `ˇ º •‰•¤
—¿ ˆ ˜ 18Ni ´ ˚ˇ ˚– —§‚ ˚ ˇ¨ ¿ ‚—ƒ
´fl¨ `¶ ,¸ ” › „ ¿ ”˜ ¨ ,˘ »fl§ ‡ • (˚ `¿
• ˚ ) ˛“ : 17. 89 % Ni ¡¢10. 10 % Co ¡¢4. 53 % Mo ¡¢
0186 % Ti ¡¢0. 12 % Al ¡¢0. 002 7 % C¡¢0. 0027 % S¡¢
01003 7 % P ,˘ ˛“ Fe ¡£ Co ”˝ Ti ”‹ `¿ ´ ‚ ,
·¸ ˘ ˙¿ ¶¨ ´ ‚ 18Ni (300) ´ ˚ˇ ˚– —§‚ ¡£ ”˜
¨ ˜ ‚ ¶§› 1200 ¡ ¡` 24 h ø ˚ »fl·ƒ , ¸ ”
1160 ¡ ¶˝ ¿“ ¯ , ¶˝ ˛´ ¶¨ ˛“ 850 ¡ , —´…¨¨ `
820 ¡ –£˛´ 1 h ” ¨¨ ,¸ ” › „ 820 ¡ ¡` 1 h „
¨ ·ƒ ” ‡ 90 mm ¿ ¡¢0. 8 mm ”æ˜ ·ł †˜ ,
– —˛`¿ (”涨 …ı—¡) • – ¿ ˘ 15 %¡¢30 %¡¢45 %¡¢
60 %”˝ 75 % ,· †»˝‹ – —˛`¿ ˜ ·ł †˜ ˇ ˙—¨¡ › ˚
ø , › ˚ ø –Œ ‡⁄ 30 mm¡¢¿ 10 mm ,˘ ‡⁄ ¶¨ •‰
ˇ ˘‰—— ˘ •‰ˇ ¡£…„⁄ ˜ ˚ ø › „ 510 ¡ ¡` 3 h
˚– —§” ¿ ¡£› ˚ Ø M TS 810 ˇ ‰ł——,…—˝• ¸
Menu
4 ˘ ¿ ‰¨ :⁄ ˇ¨ – —˛¶ ´ ˚ˇ ˚– —§‚ ˙¿ »fl˜ ˇ
¶¨ ˛“ 1 mm/ min ,ˆ¿ » · ‹ (– —˛…˚– —§) ` 3 ‚
˚ ø ,˘ ˘‰ø ˛“ › —˜ ˜ † ¶¤‰Æ„ß ¡£
· ˚– —§·ł †˜ ˇ ˙—¨¡ ˝‚ ( TEM) ˚ ø ,„ †
ˆ ˛“ ˘ ˆ ,˚ „⁄ ˜¥ ˇ ` 0. 05 mm¡£ˆ ¸« ¯ ‰…ı–¡
¯ „ ,…ı –¡ ” ˛“ 5 %‚ ‚ı ¸Æ+ 95 %˜ ˘ « ¨ ” ,–¡ ˜⁄ ˙
ˇ· ¡¢ ” ‚ ” ˆ H2800 ˝‚ „ † ,† „ 200 kV¡£
2 ¡¡ ˚ Ø ‰Æ„ߺ • ˛
2. 1 ¡¡ – —˛˙¿ »fl——˛“
˝…1 ˛“ ˚– —§˙ – —˛`¿ ¶ ˙ • ¡¢¿„ › ˙¿ ¶¨ ˜
ˇ ,¿ ¿· ‡ `‰‚ “ ˜ : ˚ ˇ¨ ˛ ´ ˚˙ •æ˚–
—§,†˜ `ˇ ˜ ˙¿ ¶¨ ¸ – —˛`¿ ˜ …¶ł ˇ ,¸ ˆ
…„⁄ ¶ ˙¿ »fl—ˆ ˇ ˜ „–ˇ ,¨ – —˛75 %˜ †˜ `ˇ
–¨ – —˛15 %˜ †˜ `ˇ ˙ • ˙¿ ¶¨ ”˝ ¿„ › ˙¿ ¶¨ ø ‚ ‡
21 % ˇ ,› „ 510 ¡ ¡` 3 h ˚– —§” ,˙ • ˙¿ ¶¨ ”˝ ¿„
› ˙¿ ¶¨ ø ‚ ‡ 11 % ˇ ¡£˘ ·˛ ,†»˝‹ – —˛`¿ ˜ †˜ `ˇ
—…‚”ı ”ª ¶¤˜ ˙ ˙¿ –¨ (– 1) ,¡ „ – —˛`¿ ˇ
† ” · ,« ˚– —§” ˙¿ ¶¨ (˙ • ¡¢¿„ › ˙¿ ¶¨ ) ˜ » …
•˙ ‡£ˇ ‰,¨ – 1 ¸ø ˚ ,› „ 510 ¡ ¡` 3 h ˚– —§” ,˙
• ˙¿ ¶¨ ˇ 890¡« 916 MPa ; ¿„ › ˙¿ ¶¨ ˇ 983¡«
1 016 MPa ¡£˚– —§” ˙¿ ¶¨ » … ¸ »œ— • †…
ˇ ˚ •¶ ˛§ ˜ ,º – —˛`¿ ˛ „ ,` » •‰ˆ ˚– —§” ˙¿ ¶¨
… ˇ ˇ –¨ ˇ´ ˇ ‰‚ 2 %¡« 3 % ,ƒ † ˚ ˛ † •¶ ˛§
˜ ¡£ ·¸ ¨ˇ ˛“ ˚– —§” ˙¿ ¶¨ ˜ » … ˚˙ ”ª ¶¤˜ ¡£
˝…1 ¡¡ – —˛¶ › ˙¿ ¶¨ ˜ ˇ
Fig. 1 ¡¡ Effect of cold rolling on tensile strength
¡¡ ¡¡ „ – —˛¶ ´ ˚ˇ ˚– —§‚ ˜ ˙¿ ¶¨ ˜ ˇ ,
˘ ˜ § ¨ˇ ˛“ ˚– —§˛ ‡ ƒ˜2Ni3 Mo ”˝ ƒ˙2Ni3
( Ti ,
Mo) ‰˚ …»fl”ˇ ˛ ˙¿ »fl , ¶ł ƒ˜2Ni3 Mo ”˝ ƒ˙2Ni3
( Ti ,
Mo) ˙ª ˇ ˛» · ˇ ˛ ‡ , ·¸ ˛» · • †…¿ ˘ ¸ ”
˚– —§˛ ‡ ˇ ˜ ˆ ¢ ¶¨ ,¶ł …„⁄ …†˜ `ˇ ˜ ˛» · ˆ
¶¨ ,˚„ ˚– —§” Ni3 Mo ”˝ Ni3
( Ti , Mo) ˛ ‡ ˇ ˆ
¢ ¶¨ …, ·¸ ˚„ †˜ `ˇ ˙¿ »fl
[ 2 ]
¡£ « – — ¿ ⁄ ˚ ,
˛ ´ – —˛`¿ ¶ · ,˚– —§” ˙¿ ¶¨ ˜ » … ”ª ¶¤ ,
– —˛†¢†»˜ · ‰ł¸ ” ˜ ˚– —§˙¿ »fl ,« – —˛˙¿ »fl
˚– —§” ¨ ¨» –£` , ·¸ ˙¿ ¶¨ ¿ ˆ ˇ´ ˚‰– · :
ƒ =ƒ
0 +ƒ⁄ƒ
CR +ƒ⁄ƒ
Age
˚‰ — ,ƒ ˛“ ˙¿ ¶¨ ;ƒ
0 ˛“ ‡ı ˚… ˙¿ ¶¨ ,¨¡ ‚ ˜ ‡
• ;ƒ⁄ƒ
CR˛“ – —˛ ˙¿ ¶¨ `¿ ,¨¡ – —˛`¿ ;ƒ⁄ƒ
Age ˛“
˚– —§ ˙¿ ¶¨ `¿ ,¨¡ ‚ ˜ ‡ • ¡£
2. 2 ¡¡ ˚– —§˛ ‡ ˇ
˝…2 ˛“ – —˛15 %¡¢510 ¡ ¡` 3 h ˚– —§ø ˘• ˛
‡ ˇ ˜ TEM ˘‹ ,˝…2 (a) ˛“ ‚· ”ˇ ˘ ,¿
¿· ‡ · ‰ˇ˙¿ ˜ ˛ ‡ ˛ ,˘ —˙¿ ª (˝…
2 ( a) — ˜ 1 ”˝ 2) …¨•ß ”ˇ ‰»‰Æ„„ ƒ˜2Ni3 Mo ˜
(211)ƒ˜, •ß ”ˇ `ø •‰‰Æ„„ƒ˙2Ni3
( Ti , Mo) ˜ (202
-
2)ƒ˙,
`‰ ˜ ˆ … ‰ˇ † 0. 05 % ,· ˇ ˛ •¤ •
– ,« ‚· ”ˇ ˘ ˇ · ¨ı ˜ (202
-
1)ƒ˙(˝…2 (a)
—˜ 3) ,⁄ ˚ `¸ `ø •‰‰Æ„„ ƒ˙2Ni3
( Ti , Mo) ˜ · ,`
» •‰ˆ , ¨ ‰—`ø •‰‰Æ„„ ƒ˙2Ni3
( Ti , Mo) · ,
(202
-
2)ƒ˙˜ ˙¿ ¶¨ ƒ ˛“ (202
-
1)ƒ˙˜ `‰–¶ ,« ¶ ‡˘
˘ — 2 ˜ ˙¿ ¶¨ –¨ 3 ˜ ˙¿ ¶¨ ‚ ‡ —¶
–¶ , ·¸ ˝…2 (a) —˙¿ ª 1 ”˝ 2 †¢•˙ ¥ ·¿ ˜ ƒ˙2
Ni3
( Ti , Mo) , ƒ ˚ ƒ˙2Ni3
( Ti , Mo) ˜ (202
-
2)ƒ˙”˝
Ni3 Mo ˜ ( 211)ƒ˜˜ ‚· ”ˇ , · ¶ł ⁄ ˚ ‰»‰Æ„„
Ni3 Mo ˜ · , ·¸ –Œ¶¤ ˛“ ˝…2 ( b) ˜ ‰Æ„ß ˚˙ ”ˇ
˜ ,…·˝…2 (a) ¸ø ˚ ˜ ‚· ”ˇ ˛“ ‰»‰Æ„„ Ni3 Mo ˜
`‰‚ – ‹ ”˝ `ø •‰‰Æ„„ Ni3
( Ti ,Mo) ˜ `‰‚ – ‹ ¡£ˆ
˝…2 (a) —˜ 1 ”˝ 2 ˆ ‰˜ ——˜ ‡¡ ˇæ• – ˛“ ˝…2
(c) ”˝ ( d) ¡£· ”˝ ˇ ƒ ˜ ‡¡ ˝…ˇæˆ ‰˜
Ni3 Mo ¡¢Ni3
( Ti ,Mo) º ´ ˚ˇ »ø ˜ ˛» ˇ „ ˇ † •ß
”ˇ —¶ ˛˜ ˇ
[ 6 ,7 ]
–¤ … ˜ ‰Æ„ß ¡£
– 1 ¡¡ › ˚ Ø ‰Æ„ß
Table 1 ¡¡ Results of tensile test
– —˛ `¿/ %
˚– —§˙ ˜ ˙¿ ¶¨ / MPa
ReL Rm ReL/ Rm
510 ¡ ¡` 3 h ˚– —§” ˜ ˙¿ ¶¨ / MPa
ReL
ƒ⁄ ReL Rm
ƒ⁄ Rm ReL/ Rm
15 1040 1 070 0. 972 1943 903 2023 983 0. 960
30 1070 1 097 0. 975 1963 893 2063 993 0. 952
45 1117 1 157 0. 965 2033 916 2133 1 016 0. 953
60 1162 1 197 0. 971 2070 908 2177 1 015 0. 951
75 1267 1 303 0. 972 2157 890 2257 990 0. 956
¡⁄ 7 6 ¡⁄
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43
(a) ¡ ˙ł ‚· ”ˇ ˘ ; ¡¡ ( b) »¤ø ‚ ˚ »fl ; ¡¡ (c) 1 ˜ ‡¡ ˇæ ; ¡¡ (d) 2 ˜ ‡¡ ˇæ
˝…2 ¡¡ – —˛15 %¡¢510 ¡ ¡` 3 h ˚– —§ø ˘• [ 001] M § ·ł Æ TEM ˘‹
Fig. 2 ¡¡ Photographs of [ 001] M zone axis of specimen 15 %reduced by cold rolling and aged at 510 ¡ for 3 h, TEM
¡¡ ¡¡ ˛“ `¸ ‰ł» †‰¨• ¨ˇ ˚– —§˛ ‡ ˇ ,· ´ ˚ˇ [ 011 ]M
§ ·ł Æ „ † ˆ ‰ ˝… 3 ¸ø ˚ ˜ ‰Æ„ß ¡£· ˝…3 (a) ˜
˘ ˇ ¿ ¿· ‡ , ˝‹ ˚– · ¶ ‚ {224
-
0}ƒ˙
§ ˆ ˜ , …¶ ‚ {202
-
0}ƒ˙§ ˆ ¨ı
(˝…3 ( a) —…˝• ¸ø ‚ ) , ·˛ ⁄ ˆ `ø •‰‰Æ„„ Ni3
( Ti ,Mo) ˜ · ,º ·¸ ˝‹ ˚– ,· ˘ ˇ „ † ‰
Ni3
( Ti ,Mo) ˜ `‰ – ‹ ,˘ —– ‹ 1 ˜ [ 112
-
0 ]ƒ˙•‰
ˇ ˘‰——[ 11
-
1 ]M ; – ‹ 2 ˜ [ 112
-
0 ]ƒ˙•‰ˇ ˘‰——[ 1
-
1
-
1 ]M § ˇ ,˝‹ ˚– · ¶ ‚ (224
-
0)ƒ˙˜ ¶ ·˛ (˝…
3 (a) —˜ 1 ”˝ 2) , ƒ˙ ˇ º ´ ˚ˇ »ø fi …˜ ˛» ˇ „
ˇ ˛“ : {110}M/ / {0001}ƒ˙, < 11
-
1 > M/ / < 112
-
0 >ƒ˙¡£
» ‰Æ„ß †¢•˙ ˛¶ ¯ †»· ‰»‰Æ„„ Ni3 Mo ¡£
˛“ · ´ ˚ˇ [ 011 ]M § ·ł Æ „ † ,Ni3 Mo ˛ ‡ ˇ ˜
” ¨ı ,‚ø Ni3
( Ti , Mo) ”˝ Ni3 Mo º ´ ˚ˇ »ø
˜ ˛» ˇ „ ˇ
[ 6 ,7 ]
, …· ( 011 )
M/ / ( 0001 )ƒ˙/ / ( 010 )ƒ˜,
[ 11
-
1 ]M/ / [ 112
-
0 ]ƒ˙/ / [ 100 ]ƒ˜,¶ł (224
-
0)ƒ˙º (400)ƒ˜ˆ
… ‰ˇ † 0. 7 % , ˚˙ ”ˇ ˜ , ·¸ ˝…4 ( b)
¸ø ˚ ˆ »› † ¨ƒ ª ˆ ‰˜ ‡¡ ˇæ˚ …˚ˇ ˚˙ (224
-
0)ƒ˙
º (400)ƒ˜‚· ”ˇ ˜ ‡¡ ˇæ ,» †»„ (400)ƒ˜ ‰ˇ
¨ı , ‡¡ ˇæ Ni3
( Ti ,Mo) ˛“ ¡£
ˆ º ˇ ˚ ˝‹ ø ˜ •‰•¤ ”˝ ˛» ˇ „ † `¸ – —˛
75 %¡¢510 ¡ ¡` 3 h ˚– —§˜ ø ˘• , ˆ ‰º – —˛
15 %ø ˘• ˇ ˝‹ ˜ ‰Æ„ß (˝…4) ,˘ • ˛ „ ‡ †» ‚ ˚ ¡£
—'‰Æ„ß– ˆ :¡ „ ˚– —§˙ ˜ – —˛`¿ †»˝‹ ,«
¡⁄ 8 6 ¡⁄
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4 ˘ ¿ ‰¨ :⁄ ˇ¨ – —˛¶ ´ ˚ˇ ˚– —§‚ ˙¿ »fl˜ ˇ
– —˛`¿ ¶ ˚– —§——˛“ ˆ» — ˆ ˇ ˜ ˇ , † —˚˙ ˚–
—§” ˙¿ ¶¨ » … †»˚ – —˛`¿ ˇ ˜ “ › ¡£
3 ¡¡ ‰Æ´
(1) ´ ˚ˇ ˚– —§‚ ˚– —§˙ – —˛,˛· ˚– —§”˝
510 ¡ ¡` 3 h ˚– —§” ˜ ˙¿ ¶¨ (˙ • ¡¢¿„ › ˙¿ ¶¨ ) ø ¸
– —˛`¿ ˜ …¶ł ˇ ¡£
(2) ˚– —§ ˘ ˜ ˙¿ ¶¨ » … ”ª ¶¤ ,º –
—˛`¿ ˛ „ , ·¸ ˙¿ ¶¨ ¿ – · ˛“ :ƒ =ƒ
0 +ƒ⁄ƒ
CR +
ƒ⁄ƒ
Age ,…·‡ı ˚…˙¿ ¶¨ ¡¢ …„⁄ ˙¿ »fl”˝ ˚– —§˙¿ »fl˜ …,
˘ —» —ƒ⁄ƒ
CR¸ – —˛ `¿ – »fl ¡£
(3) ˝‚ »¤ø … ˙¿ ¶¨ • †…
– ˆ :510 ¡ ¡` 3 h ˚– —§” ´ ˚ˇ »ø ˜ ˛ ‡ `ø •‰‰Æ
„„ ˜ Ni3
( Ti , Mo) ”˝ ‰»‰Æ„„ ˜ Ni3 Mo , – —˛
`¿ ¶ ˚– —§——˛“ ˆ» —ˆ ˇ ˜ ˇ ¡£
†˛¿…˛˜ ˇ :
[ 1] ¡¡ Rack H J , Kalish D. Improved Fatigue Resistance of 18Ni (350)
Maraging Steel Through Thermomechanical Treat ment s [J ] . Met2
allurgical Transactions , 1974 , 5 (3) :685.
[ 2] ¡¡ Roberson J A ,Adair A M. The Effect s of Prior Deformation on
t he St rengt hening Processes in Maraging Steel [ J ] . Transac2
tions of t he TMS2AIME , 1969 , 245 (9) : 1937.
[ 3] ¡¡ Ahmad Z , Farooque M , Haq A U , et al . Text ure Develop2
ment in Dual2Phase Cold2Rolled 18 pct Ni Maraging Steel [J ] .
Metallurgical Transactions , 1997 , 28A (12) : 2459.
[ 4] ¡¡ Abreu H F G, Tavares S S M , Silva J J M , et al . The Influ2
ence of an Int ermediate Austenization Heat Treat ment in t he
Text ure of Cold2Rolled and Aged 18 % Ni Maraging Steel [J ] .
Material s Characterization , 2004 , 52 (3) : 203.
[ 5] ¡¡Lee I K,Chou C P ,Cheng C M ,et al . Effect of Heat Treat ment
on Microst ruct ures of Flow Formed C2 250 Maraging Steel [J ] .
Material s Science and Technology , 2003 , 19 (11) : 1595.
[ 6] ¡¡ Tewari R ,Mazumder S ,Bat ra I S ,et al . Precipitation in 18 wt % Ni
Maraging Steel of Grade 350[J ] . Acta Materialia , 2000 , 48 (5) :
1187.
[ 7] ¡¡LI X D , YIN Z D. A Computer2Simulated Elect ron Diff raction
Analysis of Precipitates in 18Ni (350) Maraging Steel [J ] . Ma2
terial s Let t ers , 1995 , 23 (426) : 269.
(ˇ ‰ 60 ‡ )
¡¡ ¡¡ (3) ˝¤ „ ˜' ·˛ …˘¸ª ‡ ¿ ”涨 ˜ †¤¶fl¿ ˚¶ –
† „⁄ ¨¸ ˜ ¿¤`¿ •· ¡ …‚ ¯ ˜ ‚ ‡£ ,· ¶ł ¨¥
‡ » „ؘ – ¿„ `ƒ †˛ ˚ —˜ †»`…˚ ,–£‡ ˚ ˜ ¯
`…—¡£
(4) ˚ …˚ƒ ˆ – ˆ ,‚ˆ ˚˚ ƒ ˘ ˜£ —˝¿
˛ † ”æ˙ ˇ´ ˛¨ ¶¤˜ ˚ ˇ ˘ `ƒ ˜ ‚ « ¶¨ ⁄ –¤ ,‚ˆ ˜£
—˝˜ ˘ `ƒ ⁄ † ˘« † ¿ ¿ ˘ 7 % ˜ ,˘ —
˘ `ƒ ⁄ † ˘« † 5 % ˜ ˜ ·˛ ¿ … 73 % ˇ ,‡
¿ ”涨 ˜ ⁄ …˘¸ª ˘« † » ª ¿ ¿ ˘ 0. 2 mm
˜ , —” ˙¿ ˜ ˚ ˆ —¡£
†˛¿…˛˜ ˇ :
[ 1] ¡¡ ”œˇ˝ , ¡¡ , ‰ˆ ‰, ¨ . —”æ ”æ¶¨ ˜ ˇ ¨ † `¿ •‰•¤
[J ] . ‚ œ —¿ § –¤ , 2006 , 18 (7) : 55. ( HU Xian2lei , ZHAO
Zhong , J IAO Zhi2jie , et al . On2Line Soft2Mearsuring Met hod
of Plate Thickness [ J ] . Journal of Iron and Steel Research ,
2006 , 18(7) :55. )
[ 2] ¡¡ ”œˇ˝ ,˙æ” ,`ı ˇ »“ ,¨ . —”æ fl ł ˙œˇ `ª ª ˘fl ˘ ¶
˘ `ƒ ˚˚ ƒ ˜ ˇ [ J ] . ‚ œ —¿ § –¤ , 2003 , 15 ( 1) : 24.
( HU Xian2lei , QIU Hong2lei , LIU Xiang2hua , et al . Influence
of Zero Wave for Spring Curve on Rolling Force Adaption in
Plate Rolling[J ] . Journal of Iron and Steel Research , 2003 , 15
(1) :24. )
¡⁄ 9 6 ¡⁄
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Control of High Strength Low Alloy (HSLA) Steel Properties
Abstract:
Most HSLA steels are furnished in the as-hot-rolled condition with ferritic-pearlitic microstructure. The
exceptions are the controlled-rolled steels with an acicular ferrite microstructure and the dual-phase steels
with martensite dispersed in a matrix of polygonal ferrite. These two types of HSLA steels use the formation
of eutectoid structures for strengthening, while the ferritic-pearlitic HSLA steels generally require
strengthening of the ferrite.



Most HSLA steels are furnished in the as-hot-rolled condition with ferritic-pearlitic microstructure. The
exceptions are the controlled-rolled steels with an acicular ferrite microstructure and the dual-phase steels
with martensite dispersed in a matrix of polygonal ferrite. These two types of HSLA steels use the formation
of eutectoid structures for strengthening, while the ferritic-pearlitic HSLA steels generally require
strengthening of the ferrite.
Pearlite is generally an undesirable strengthening agent in structural steels because it reduces impact
toughness and requires higher carbon contents. Moreover, yield strength is largely unaffected by a higher
pearlite content.
Strengthening Mechanisms in Ferrite
The ferrite in HSLA steels is typically strengthened by grain refinement, precipitation hardening, and, to a
lesser extent, solid-solution strengthening. Grain refinement is the most desirable strengthening
mechanism because it improves not only strength but also toughness.
Grain refinement is influenced by the complex effects of alloy design and processing methods. For
example, the various methods of grain refinement used in the three different stages of hot rolling (that is,
reheating, hot rolling, and cooling) include:
ƒ The addition of titanium or aluminum to retard austenite grain growth when the steel is reheated for
hot deformation or subsequent heat treatment
ƒ The controlled rolling of microalloyed steels to condition the austenite so that it transforms into
fine-grain ferrite
ƒ The use of alloy additions and/or faster cooling rates to lower the austenite-to-ferrite transformation
temperature.
The use of higher cooling rates for grain refinement may require consideration of its effect on precipitation
strengthening and the possibility of undesirable transformation products.
Precipitation strengthening occurs from the formation of finely dispersed carbonitrides developed during
heating and cooling. Because precipitation strengthening is generally associated with a reduction in
toughness, grain refinement is often used in conjunction with precipitation strengthening to improve
toughness.
Precipitation strengthening is influenced by the type of carbonitride, its grain size, and, of course, the
number of carbonitrides precipitated. The formation of MC is the most effective metal carbide in the
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precipitation strengthening of microalloyed niobium, vanadium, and/or titanium steels. The number of fine
MC particles formed during heating and cooling depends on the solubility of the carbides in austenite and
on cooling rates.
Steelmaking
Precise steelmaking operations are also essential in controlling the properties and chemistry of HSLA
steels. Optimum property levels depend on such factors as the control of significant alloying elements and
the reduction of impurities and nonmetallic inclusions.
Developments in secondary steelmaking such as desulphurization, vacuum degassing, and argon
shrouding have enabled better control of steel chemistry and the effective use of microalloyed elements.
Compositional limits for HSLA steel grades described in ASTM specifications the use of vacuum degassing
equipment allows the production of interstitial-free (IF) steels. The IF steels exhibit excellent formability,
high elongation, and good deep draw/ability.
Compositions and Alloying Elements
Chemical compositions for the HSLA steels are specified by ASTM standards. The principal function of
alloying elements in these ferrite-pearlite HSLA steels, other than corrosion resistance, is strengthening of
the ferrite by grain refinement, precipitation strengthening, and solid-solution strengthening. Solid-solution
strengthening is closely related to alloy contents, while grain refinement and precipitation strengthening
depend on the complex effects of alloy design and thermo-mechanical treatment.
Alloying elements are also selected to influence transformation temperatures so that the transformation of
austenite to ferrite and pearlite occurs at a lower temperature during air cooling. This lowering of the
transformation temperature produces a finer-grain transformation product, which is a major source of
strengthening. At the low carbon levels typical of HSLA steels, elements such as silicon, copper, nickel, and
phosphorus are particularly effective for producing fine pearlite. Element such as, manganese and
chromium, which are present in both the cementite and ferrite, also strengthen the ferrite by solid-solution
strengthening in proportion to the amount, dissolved in the ferrite.
In the presence of alloying elements, the practical maximum carbon content at which HSLA steels can be
used in the as-cooled condition is approximately 0.20%. Higher levels of carbon tend to form martensite or
bainite in the microstructure of as-rolled steels, although some of the higher-strength low-alloy steels have
carbon contents that approach 0.30%.
The required strength is developed by the combined effect of:
• Fine grain size developed during controlled hot roiling and enhanced by microalloyed elements
(especially niobium)
• Precipitation strengthening caused by the presence of vanadium, niobium, and titanium in the
composition.
Nitrogen additions to high-strength steels containing vanadium are limited to 0.005% and have become
commercially important because such additions enhance precipitation hardening. The precipitation of
vanadium nitride in vanadium-nitrogen steels also improves grain refinement because it has a lower
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solubility in austenite than vanadium carbide.
Manganese is the principal strengthening element in plain carbon high-strength structural steels. It
functions mainly as a mild solid-solution strengthener in ferrite, but it also provides a marked decrease in
the austenite-to-ferrite transformation temperature. In addition, manganese can enhance the precipitation
strengthening of vanadium steels and. to a lesser extent, niobium steels.
One of the most important applications of silicon is its use as a deoxidizer in molten steel. Silicon has a
strengthening effect in low-alloy structural steels. In larger amounts, it increases resistance to scaling at
elevated temperatures. Silicon has a significant effect on yield strength enhancement by solid-solution
strengthening and is widely used in HSLA steels for riveted or bolted structures.
Copper in levels in excess of 0.50% also increases the strength of both low- and medium-carbon steels by
virtue of ferrite strengthening, which is accompanied by only slight decreases in ductility. Copper can be
retained in solid solution even at the slow rate of cooling obtained when large sections are normalized, but it
is precipitated out when the steel is reheated to about 510 to 605°C (950 to 1125°F). At about 1% copper,
the yield strength is increased by about 70 to 140 MPa regardless of the effects of other alloying elements.
Copper in amounts up to 0.75% is considered to have only minor adverse effects on notch toughness or
weldability. Copper precipitation hardening gives the steel the ability to be formed extensively and then
precipitation hardened as a complex shape or welded assembly.
The atmospheric-corrosion resistance of steel is increased appreciably by the addition of phosphorus, and
when small amounts of copper are present in the steel, the effect of the phosphorus is greatly enhanced.
When both phosphorus and copper are present, there is a greater beneficial effect on corrosion resistance
than the sum of the effects of the individual elements.
Chromium is often, added with copper to obtain improved atmospheric-corrosion resistance.
Nickel is often added to copper-bearing steels to minimize hot shortness.
Molybdenum in hot-rolled HSLA steels is used primarily to improve hardenability when transformation
products other than ferrite-pearlite are desired. Molybdenum (0.15 to 0.30%) in microalloyed steels also
increases the solubility of niobium in austenite, thereby enhancing the precipitation of NbC(N) in the ferrite.
This increases the precipitation-strengthening effect of NbC(N).
Aluminum is widely used as a deoxidizer and was the first element used to control austenite grain growth
during reheating. During controlled rolling, niobium and titanium are more effective grain refiners than
aluminum.
Vanadium strengthens HSLA steels by both precipitation hardening the ferrite and refining the ferrite grain
size. The precipitation of vanadium carbonitride in ferrite can develop a significant increase in strength that
depends not only on the rolling process used, but also on the base composition. Carbon contents above
0.13 to 0.15% and manganese content of 1% or more enhances the precipitation hardening, particularly
when the nitrogen content is at least 0.01%.
Titanium is unique among common alloying elements in that it provides both precipitation strengthening
and sulfide shape control. Small amounts of titanium (<0.025%) are also useful in limiting austenite grain
growth. However, it is useful only in fully killed (aluminum deoxidized) steels because of its strong
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deoxidizing effects, the versatility of titanium is limited because variations in oxygen, nitrogen, and sulfur
affect the contribution of titanium as carbide strengthened.
Zirconium can also be added to killed high-strength low-alloy steels to improve inclusion characteristics,
particularly in the case of sulfide inclusions, for which changes in inclusion shape improve ductility in
transverse bending.
Boron has no effect on the strength of normal hot-rolled steel but can considerably improve hardenability
when transformation products such as acicular ferrite are desired in low-carbon hot-rolled plate.
Treatment with calcium is preferred for sulfide inclusion shape control.
Controlled Rolling
The hot-rolling process has gradually become a much more closely controlled operation, and controlled
rolling is now being increasingly applied to microalloyed steels with compositions carefully chosen to
provide optimum mechanical properties at room temperature.
Controlled rolling is a procedure whereby the various stages of rolling are temperature controlled, with the
amount of reduction in each pass predetermined and the finishing temperature precisely defined. This
processing is widely used to obtain reliable mechanical properties in steels for pipelines, bridges, offshore
platforms, and many other engineering applications. The use of controlled rolling has resulted in improved
combinations of strength and toughness and further reductions in the carbon content of microalloyed HSLA
steels.


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SUSCEPTIBILITY TO BRITTLE FRACTURE
OF FLANGES IN ASTM A105.
A. Dhooge and E. Deleu, Research Center of the Belgian Welding Institute (BWI)
ABSTRACT
The incentive for the present study was a brittle fracture that occurred in a 101 mm
thick 24” welding neck flange of Class 600 according to ANSI B16.5. This
component, with a coarse grain microstructure, was installed in a high-density
polyethylene (HDPE) loop reactor and failed presumably at a temperature of -16 °C.
In this project, a large number of ASTM A105 carbon steel flanges has been
investigated with the main purpose of evaluating the material’s fracture toughness
and defect tolerance. Investigations revealed large variations in microstructure, grain
size and hardness, depending on the manufacturing route and heat treatment. Even
multiple small hydrogen cracks were found in two of the investigated 24” flanges.
Toughness has been evaluated by notch impact and CTOD fracture toughness tests
at different low temperatures. A correlation was made between microstructure, grain
size and fracture toughness. A fitness-for-purpose analysis, based on CTOD fracture
toughness, allowed to assess the risk for brittle fracture in large (24” / Class 600)
carbon steel flanges complying with ASTM A105.
1. INTRODUCTION
Codes, ASME VIII div.1 and ASME B31.3 allow carbon steel conforming to
ASTM A105 [1] for applications down to a minimum temperature of -29 °C (-20 °F).
In January 1998, Borealis Beringen (Belgium) experienced brittle fracture in a raised
face 101 mm thick 24” welding neck flange of Class 600 operating in the loop of a
reactor of an HDPE-unit since 1990. Due to a power dip in the plant, the product in
the reactor boiled at atmospheric pressure, resulting in cooling of the reactor and the
loop to about -16 °C. The line was partly plugged with solid product at the location of
the failed flange, which resulted in an uneven cooling of this flange. It was assumed
that, close to the boiling product, the temperature of the flange was about –16 °C but
about +60 °C at the location of the plug, see Figure 1. The flange cracked at the
transition between the conical and cylindrical part of the welding neck, see Figure 2,
at a location coinciding with the cold area.
Previous investigations at the Belgian Welding Institute (BWI) revealed that the
flange had a coarse grained (ASTM grain size number 5 to 6) ferrite-pearlite
microstructure, see Figure 3. The 27 J Charpy-V impact transition temperature was
about +10 °C. An additional heat treatment at BWI (normalising at 900 °C for one
hour) resulted in grain refinement to ASTM grain size number 9, see Figure 4, and in
a shift of impact transition temperature to below -30 °C.
As a result of this, a research project has been initiated with the following main
objectives:
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- to get a better understanding of the relation between microstructure, grain size,
hardness and fracture toughness properties of flanges in carbon steel
complying with ASTM A105
- to formulate recommendations and requirements for flanges actually in use in
different plants as well as for new installations.
2. INVESTIGATED MATERIAL
Within the scope of a fitness-for-purpose analysis, a series of flanges with different
sizes and of various rating classes has been fully characterised.
To achieve this, the fractured 24” / Class 600 flange from Borealis (symbolised
hereafter by FLA) has been retained for further investigation as well as two other
flanges of same size and rating class (symbolised by FLB and FLD), which were
removed from the HDPE reactor. Moreover, twenty new flanges with different sizes
and rating classes, manufactured in carbon steel conforming to ASTM A105 have
been ordered at one supplier (stockist). Flanges were obtained from three different
manufacturers together with EN10204:3.1B certificates.
An overview of all investigated welding neck flanges and most important topics is
given in Table 1. According to the relevant certificates, all flanges received a
normalising heat treatment after forging, which, according to ASTM A105, is only
mandatory for flanges above Class 300.
3. TEST PROGRAMME AND RESULTS
The investigation of in total twenty-three flanges included chemical analyses,
metallographic examinat