PROCESSING OF Cu-Cr ALLOY BY CRYO

ROLLING: STRUCTURE – PROPERTY

CORRELATION

A thesis submitted in partial fulfillment of the requirements for the

award of the degree of

M. Tech

In

MATERIALS SCIENCE AND ENGINEERING

By

VANKAYALA SATYAM

DEPARTMENT OF METALLURGICAL AND

MATERIALS ENGINEERING

NATIONAL INSTITUTE OF TECHNOLOGY

TIRUCHIRAPPALLI – 620015

DECEMBER 2020
 BONAFIDE CERTIFICATE

This is to certify that the project titled “PROCESSING OF Cu-Cr ALLOY BY CRYO
ROLLING: STRUCTURE – PROPERTY CORRELATION” is a bonafide record
of the work done by

VANKAYALA SATYAM (212219019)

in partial fulfillment of the requirements for the award of the degree of Master of
Technology in Materials Science and Engineering of the NATIONAL INSTITUTE
OF TECHNOLOGY, TIRUCHIRAPPALLI, during the year 2019-2020.

Dr. S. Kumaran
Project Guide
Head of Department,MME

NIT Tiruchirappalli

Project Viva-voce held on……………………….

Internal Examiner External Examiner

ii
 ABSTRACT

Ultrafine grained (UFG) materials are of interest because it provides the combination of
high strength and ductility compared with coarse grained counterparts. Several current
methods are employed to fabricate UFG materials which results in samples too small for
practical applications. Severe plastic deformation (SPD) processes like Equal-channel
angular pressing (ECAP), accumulative rolling bonding (ARB) and high-pressure torsion
(HPT) produces ultrafine grained microstructure at the cost of electrical conductivity.
Besides SPD processes, cryorolling provides an opportunity to obtain ultrafine grained
materials with high density of dislocations for improving mechanical properties.
Cryorolling is rolling of material at cryogenic temperatures like liquid nitrogen
temperature (LNT). Cu-Cr alloy is to be solutionized at 960°C for 15 minutes and
subjected to cryorolling up to 70% thickness reduction and same with cold-rolling along
with intermediate aging is to be performed at 450°C for 2hrs for both the rolling
processes. Analyzing the results from different characterization techniques such as optical
microscopy, TEM, XRD, micro tensile test, Micro Vickers hardness test has to be done.
Studies showing that cryorolled with intermediate aging gives high tensile strength among
all other samples done by the above processes because of combined effect of twinning,
precipitation hardening due to Cr particles and grain boundary strengthening. The minor
additions of Zirconium and Chromium to copper reduces the stacking fault energy of
copper by widening of width of two partial screw dislocations which results in twinning
of crystallographic planes.

Key words: Cu-Cr alloy, cyrorolling, precipitation hardening, TEM, tensile test, hardness
test.

iii
 ACKNOWLEDGEMENT

I express my deep sense of gratitude to my Project Guide Dr. S. Kumaran, Professor

and Head, Department of Metallurgical and Materials Engineering, National Institute of
Technology, Tiruchirappalli for this consistent support and motivation throughout the
project. I thank him for his patience and guidance which will led to the successful
completion of this project.

I sincerely thank Dr. Mini Shaji Thomas, Director, National Institute of Technology,
Tiruchirappalli, and Dr.S.Kumaran, Professor and Head, Department of Metallurgical
and Materials Engineering, National Institute of Technology, Tiruchirappalli, for
permitting me to carry out the project in the campus.

I would like to thank all the teaching and non-teaching faculties from the Department of
Metallurgical and Materials Engineering, National Institute of Technology,
Tiruchirappalli, for their consistent support.

VANKAYALA SATYAM

iv
 TABLE OF CONTENTS
chapter no. title page no.
ABSTRACT…………………………………………………………….......
ACKNOWLWDMENTS………………………………………………….
TABLE OF CONTENTS………………………………………………….
LIST OF TABLES………………………………………………………....
LIST OF FIGURES……………………………………………………….
CHAPTER 1 INTRODUCTION
1.1 COPPER AND ITS ALLOYS ………………………………………...1
1.2 CRYOROLLING…………………………………………………….. 4
1.3 HEAT TREATMENT TECHNIQUES………….................................5
1.3.1 ANNEALING………………………………………………………....5
1.3.2 NORMALIZING……………………………………………………..6
1.3.3 HARDENING……………………………………………………..6
1.3.4 TEMPERING……………………………………………………..6
1.3.5 PRECIPITATION HARDENING…………………………………..6
1.3.6 AGING………………………………………………………………..7

CHAPTER 2 LITERATURE REVIEW 9

CHAPTER 3 OBJECTIVES 25

CHAPTER 4 WORKPLAN 26

CHAPTER 5 REFERENCES 28

v
 LIST OF TABLES
TABLE NO. TITLE PAGE NO.
1.1 Physical Properties of Copper 2
2.1 comparison of mechanical properties of cryorolled Cu-1.5%Ti
And RT rolled Cu-1.5%Ti alloy 17
2.2 rolling-aging routes 23

vi
 LIST OF FIGURES
FIGURE NO. TITLE PAGE NO.
2.1 strees strain curve for pure copper and Cu-12.1at.%Al-4.1at.%Zn …....10

2.2 TEM micrograph of pure copper sample rolled at 77K. …………..…….10

2.3 TEM micrograph of Cu–12.1%Al–4.1%Zn sample rolled at 77K. …….10

2.4 TEM image obtained at the grain boundaries of the aged Cu-Cr-Zr alloy.

…11

2.5 Microstructure of alloy after ESR process ………………………………12

2.6 XRD test for 20% and 40%thickness for copper ………………………..13

2.7 hardness chart for copper ………………………………………………...14

2.8 Light micrograph of solutionized plus aged alloy ……………………….18

2.9 DF micrograph showing a large chromium particle ……………………18

2.10 Hardness vs aging time and temperature of (a)SSA (b) RSA. ………..19

2.11 Hardness with regard to time aged at 500°C ………………………….20

2.12 Hardness with regards to strain aged for 2h …………………………..20

2.13 Scanning electron micrographs showing the microstructures of Cu-

0.76Cr-0.13Zr alloy after being ………………………………………..20

2.14 Engineering stress–strain curves of (a) pure copper and (b) CuCrZr alloy

…..21

2.15 SEM micrographs of the samples: a) as sintered, b) sintered, solution-

treated, quenched and aged for 8hr …………………………………..22

2.16 XRD patterns of the sinter-pressed sample and the sintered, solution-

treated, quenched and aged samples …………………………………..23

2.17 Bright field TEM Images showing deformation twins and Cr precipitates

(heat treatment) …………………………………………………………24

2.18 tensile test and electrical conductivity results ……………………… 25

vii
 CHAPTER 1
INTRODUCTION

Little is known about the human being. Altogether, humans want to fly and discover the
universe. For this purpose, they need materials science. A droplet of this science will be
included in the present study.

1.1 COPPER AND ITS ALLOYS

To survive in the high-temperature, high-pressure environment of today's rocket
engines, the combustion chamber hot-gas wall must be fabricated from a high thermal
conductivity material and must be actively cooled. The cryogenic engine combustion
chamber is a milled channel design in which coolant channels are machined into the
outside surface of the chamber liner. Then these channels are closed out by brazing to
stainless steel outer to form coolant passages. Due to the severity of in-service loading
conditions materials used in fabrication of thrust cell liners must exhibit high thermal
conductivity, high strength good low cycle fatigue (LCF) life and creep resistance. Few
materials naturally possess all these characteristics. A few copper-based alloys have,
however, been developed specifically for use in high-performance rocket nozzles.

Copper is a chemical element with symbol Cu (from Latin: cuprum) and atomic
number 29 and atomic radius of 128pm.The chemical element is classed as a transition
metal. It is in group 11, period 4 of the periodic table. Copper is non -polymorphous
metal with face centered cubic (FCC) lattice. Copper ranks as third-most-consumed
industrial metal in the world, after iron and aluminum. About three-quarters of that
copper goes to make electrical wires, telecommunication cables and electronics. Of all
the metals, copper is the one most likely to be found in its native state, often released by
the chemical reaction of its ores. The main properties of Copper are:

Good Electrical Conductivity : Copper has the best electrical conductivity of

any metal, except silver. A good electrical conductivity is the same as a small
electrical resistance. Therefore, copper wires are used in mains cables in houses and
underground (although overhead cables tend be aluminium because of its less dense).

Good Thermal Conductivity: Copper is a good conductor of heat. Most metals

are pretty good conductors; however, apart from silver, copper is the best. It is used in

1
many heating applications because it does not corrode and has a high melting point.

Corrosion Resistance: Copper is low in the reactivity series. This means that it
does not tend to corrode. This is important for its use for pipes, electrical cables,
saucepans and radiators because of high corrosion resistance.

Antimicrobial: Copper is inherently antimicrobial, meaning it will rapidly kill

bacteria, viruses and fungi that settle on its surface. This property is seeing the
installation of surfaces made from copper and copper alloys in hospitals and other areas
where hygiene is a key concern.

Easily Joined: Copper can be joined easily by soldering or brazing. This is useful
for pipework and for making sealed copper vessels.
Ductile: Copper is a ductile metal. This means that it can easily be shaped into pipes
and drawn into wires. Copper pipes are lightweight because they can be formed into thin
walls. They do not corrode, and they can be bent to fit around corners. The pipes can be
joined by soldering and they are safe in fires because they d on't catch fire or support
combustion.

Tough: Copper and copper alloys are tough. This means that they were well suited
to being used for tools and weapons. The property of toughness is vital for copper and
copper alloys in the modern world. They do not shatter when they are dropped or become
brittle when cooled below 0°C.

Non-magnetic: Copper is non-magnetic and non-sparking. Because of this, it is

used in special tools and military applications.

Table 1.1 Physical Properties of Copper

Phase (STP ) Solid

Melting Point 1084.62 0C
Boiling Point 2562 0C
Density 8.96g/cm 3
Heat of Fusion 13.26kJ/mol
Heat of Vaporisation 300kJ/mol

In their pure form many metals have vulnerabilities such as low melting points, low
creep resistance or high temperature characteristics. When two metals or elements are
2
combined though they form an alloy. Small amounts of alloying elements are often
added to metals to improve certain characteristics of the metal. Alloying can increase or
reduce the strength, hardness, electrical and thermal conductivity, corrosion resistance,
or change the color of a metal. [3]

Through alloying the high-temperature performance of copper is improved, resulting in

increased strength and creep resistance. The alloy used to fabricate the cryogenic engine
is made of age hardenable chromium copper alloy containing traces of Zr and Ti.
Chromium copper alloys are high copper alloys. The chromium copper alloys used for
their high strength, electrical conductivity and corrosion resistance. The chromium
copper alloys are age hardenable, which in this case, means that a change in properties
occurs at elevated temperature due to the precipitation of chromium out of solid solution.
The strength of fully aged chromium copper is nearly twice that of pure copper and its
electrical conductivity remains high at 85% IACS or 85% of pure copper. These high
strengths retain their strength at elevated temperatures. The corrosion resistance of
chromium copper alloy is better than that of pure copper because chromium improves
the chemical properties of protective oxide film. Chromium copper has excellent
formability and good hot workability. It is used in applications such as resistance
welding electrodes, seam welding wheels, switch gears, cable connectors, circuit
breaker parts, molds, spot welding tips, and electrical and thermal conductors that
require strength .

The ductility of these alloys near the expected use temperatures of 400° to 600°C
has been found to be poor compared to other copper alloys. This is because of dynamic
embrittlement characterized by inter-granular fracture caused by stress induced ingress
of Sulphur[S] to the grain boundaries followed by decohesion, especially during hot
deformation processing between 200° to 500°C. Cu-Cr-Zr-Ti alloy responds well to heat
treatment and good improvement in strength can be achieved by combination of solution
treatment and aging. The strengthening phase in aged condition was reported as nano-
sized chromium rich bcc precipitates. The present alloy is a modified version of binary
Cu-Cr alloy with minor addition of zirconium and titanium to ensure good ductility at
intermediate temperature by formation of sulphides. Thus, addition of Zr and Ti results
in no dynamic embrittlement due to presence of small titanium-sulphide and zirconium-
sulphide at grain boundaries in place of S thus increasing the ductility and boundary
strength. (S. Zhang et al., 2017)

3
 Generally, solute atoms in the copper matrix inevitably deteriorate the electrical
conductivity of alloys. Therefore, precipitation strengthened copp er alloys are
developed to achieve an optimized combination of wear reistance, electrical
conductivity and strength through aging treatment. To more specific, the Cu-Cr-Zr
alloys, as the typical precipitation strengthened copper alloys, have been used in v ariety
of applications such as railway contact wire.

In recent years, severe plastic deformation (SPD) processes such as equal

channel angular pressing (ECAP), high-pressure torsion (HPT), and accumulative
rolling bonding (ARB) produce series of ultrafine grained copper alloys with superior
mechanical properties. High density of grain boundaries and high strains introduced by
SPD process has significant effect on strengthening along with little effect on the
electrical conductivity. Aging process has also been implemented after SPD to promote
precipitation hardening and improve conductivity in copper alloys. Besides SPD
processes, cryorolling, i.e., rolling at liquid nitrogen temperature (LNT) has been
attempted on several metals and alloys to obtain ultrafine grained materials with high
density of dislocations for improving mechanical properties.

1.2 CRYOROLLING
Cryogenic rolling or cryorolling, is one of the potential techniques to produce
nanostructured bulk materials (nano crystalline) from its bulk counterpart at cryogenic
temperatures. It can be defined as rolling that is performed at cryogenic temperatures.
Nanostructured materials are produced chiefly by severe plastic deformation processes
which require large plastic deformations. In case of cryogenic rolling, the deformation
in the strain hardened metals is preserved as a result of the suppression of the dynamic
recovery. Hence large strains can be retained, and ultra-fine-grained structure can be
produced after post annealing.

Advantages of cryorolling over room temperature rolling

1. High dislocation density can be achieved by effectively suppressing the cross slip and
climb of dislocations which cannot be observed in case of room temperature rolling.

2. Involving of high residual stresses comparatively decrease in corrosion resistance of

cryorolled sample.

3. Cryorolled sample shows higher flow stress when compared to sample rolled at room

4
 temperature (RT).

4. Significant decrease in electrical conductivity can be observed in cryorolled sample due

to increase in number of electron scattering centres.

5. After subsequent annealing of cryorolled samples ultra-fine-grained structures can be

produced.

6. At room temperature, dynamic recovery is inevitable, and softening takes place where
as in cryorolling, the strain hardening is retained up to the extent to which rolling is
carried out that is no dynamic recovery and dislocation annihelation. (J.T. Shi et al.,
2017)

1.3 HEAT TREATMENT TECHNIQUES

Heat treating (or heat treatment) is a group of industrial and metalworking processes
used to alter the physical, and sometimes chemical, properties of a material. The most
common application is metallurgical engineering. Heat treatments are also used in the
manufacture of many other materials, such as glass, ceramics. Heat treatment involves
the use of heating or chilling, normally to extreme temperatures, to achieve a desired
result such as hardening or softening of a material.
Metallic materials consist of a microstructure of small crystals called "grains" or
crystallites. The nature of the grains (i.e., grain size and composition) is one of the most
important factors that can determine the overall mechanical behavior of the metal. Heat
treatment provides an efficient way to change the properties of the metal by controlling
the rate of diffusion and the rate of cooling within the microstructure. Heat treating is
often used to alter the mechanical properties of a metallic alloy, optimizing property
such as hardness, strength, toughness, ductility, and elasticity.
Various types of heat treatment processes are:

1.3.1 ANNEALING

Annealing is one of the most important heat treatment process applied to steel. It is the
process of heating the steel in a furnace to a point not exceeding 50° above its upper
critical point and maintaining the steel at that temperature for a considerable time (30-
60 minutes) to convert the whole steel to austenite. Steel is supposed to cool down slowly

5
through a medium of hot sand, hot ashes or hot lime dust. The rate of cooling is to be
maintained at 150-200ºC per hour. It is a slow cooling process and in general furnace
cooling is employed.

1.3.2 NORMALIZING

The process consists of heating of steel to a point 40 to 50°C above its upper critical
temperature. Hold at that temperature for a short duration and then cooling in still air at
room temperature. This is also known as air quenching. It produces microstructures
consisting of ferrite and pearlite for hypo-eutectoid steels and pearlite and cementite for
hyper-eutectoid steels. Relatively fine-grained microstructure can be obtained when
compared to annealing.

1.3.3 HARDENING

In hardening process, the alloy is first heated to a point exceeding 50ºC above the upper
critical point for hypo-eutectoid steels and 30-50ºC above for hyper-eutectoid steel.
Then the alloy is soaked at this temperature for a considerable time to ensure that all the
pearlite and cementite have changed into austenite and then the steel is cooled rapidly to
keep the austenite to remain as such at room temperature. This process consists of two
operations – heating and quenching. Between 300-200ºC martensite is formed. This in
turn, causes an increase in the volume of the metal thereby developing high internal
stresses and strains in the final product.

1.3.4 TEMPERING

It is a process of heat treating, which is used to increase the toughness of iron-based

alloys. Tempering is usually performed after hardening, to reduce some of the excess
hardness, and is done by heating the metal to some temperature below the critical point
for a certain period of time, then allowing it to cool in still air. The exact temperature
determines the amount of hardness to be decreased and depends on both the specific
composition of the alloy and on the desired properties in the finished product.

6
1.3.5 PRECIPITATION HARDENING

Precipitation hardening, also called age or particle hardening, is a heat treatment process
that produces uniformly dispersed particles within a metal matrix. These particles hinder
dislocation motion and thereby strengthen the metal, particularly those that are
malleable.

Precipitation hardening alloys first came into use during the early 1900s. Most heat-
treatable alloys fall into the category of precipitation hardening alloys,
including alloys of aluminum, magnesium, titanium and nickel. Several high-alloy
steels are also precipitation hardening alloys. These alloys become softer than normal
when quenched, and then harden over the time passes. For this reason, precipitation
hardening is often referred to as "aging."

Although most precipitation hardening alloys will harden at room temperature, some
will only harden at elevated temperatures and, in others, the process can be speed up by
aging at elevated temperatures. Aging at temperatures higher than room-temperature is
called "artificial aging". Although the method is similar to tempering, the term
"tempering" is usually not used to describe artificial aging, because the physical
processes, (i.e., precipitation of intermetallic phases from a supersaturated alloy) the
desired results, (i.e.: strengthening rather than softening), and the amount of time held
at a certain temperature are very different from tempering as used in carbon-steel.

The aging process is one of the three important steps involved in precipitation hardening,
the other two being - solution treatment and quenching. During precipitation heat
treatment, the supersaturated solution is heated to an intermediate temperature to induce
precipitation and held at that temperature for a specific amount of time and then
immediately quenched in quenching media.

1.3.6 AGING

Some metals are classified as precipitation hardening metals. When a precipitation

hardening alloy is quenched, its alloying elements will be trapped in solution, resulting
in a soft metal. Aging a "solutionized" metal will allow the alloying elements to diffuse
through the microstructure and form intermetallic particles. These intermetallic particles
will nucleate and fall out of solution and act as a reinforcing phase, thereby increasing

7
the strength of the alloy. Alloys may age "naturally" meaning that the precipitates form
at room temperature, or they may age "artificially" when precipitates only form at
elevated temperatures.

Different Aging Techniques

Artificial Aging: Artificial aging is the treatment of a metal alloy at elevated

temperatures to accelerate the changes in the properties of an alloy as a result of the
casting and forging process. Generally, the chemical properties of newly cast and forged
metals naturally change and settle very slowly at room temperature. Artificial aging will
speed up this change more rapidly at higher temperatures. This process ensures quality
and accuracy in close tolerance specifications. It also helps manufacturers m ake
machine-ready parts available much more quickly to machinists and distributors.

Natural Aging: Aging that occurs at room temperature is referred as natural aging.

Aging is an essential step that ensures that the materials in the alloy do not revert to their
original configuration after a time period. Aging is performed under controlled
conditions so that the resultant grain structure will create a greater tensile strength in the
metal than in its former state. To achieve peak hardness in natural aging it requires long
period of time.

BENEFITS OF AGING

Aging not only helps to enhance high strength of alloys but helps them to acquire other
valuable properties such as high coercively. In addition, aging tends to restore the
equilibrium in the metal and to eliminate any unstable conditions brought upon by a
prior operation.

It has been shown that deformation and aging greatly reduce the resilience and ductility
of alloys. However, the adverse effects of aging can be reduced to a large extent by
optimizing alloying and heat treatment.

8
 CHAPTER 2
LITERATURE REVIEW

[1] H. Bahmanpour, A. Kauffmann, M.S. Khoshkhoo, K.M. Youssef, S. Mulaa, J.

Freudenberger, J. Eckert, R.O. Scattergooda, C.C. Koch, Effect of stacking fault
energy on deformation behavior of cryo-rolled copper and copper alloys (2011)

Pure copper and Cu-12.1at.%Al-4.1at.%Zn alloy were subjected to rolling in liquid

nitrogen. TEM studies showed that dynamic recovery during the deformation process
was effectively suppressed and hence microstructures with dislocation substructure and
deformation twins were identified. Alloying with Al and Zn results in reduction in
stacking fault energy (SFE) which can contribute to enhanced strength and good
ductility twinning will occur rather than slip. To homogenize the composition of the
alloy, samples were kept at 800°C for 14 h under argon atmosphere. Hot rolling was
done by preheating to 600°C and rolling from 25mm to 20.5mm to remove the cast
microstructure. Another homogenization step was done at 800°C for 14 h under argon
atmosphere and subsequent water quenching to avoid short range ordering. The
samples exhibit grain sizes of several hundred micrometers, and mostly random
distribution of grain orientations.

Samples measuring 10 mm × 10 mm × 10 mm were cut from hot-rolled ingots and

soaked in liquid nitrogen to reach the 77K. In order to effectively suppress the dynamic
recovery and recrystallization during the deformation process; the samples are kept in
LNT both before after the rolling is performed. All compositions were rolled to about
90% reduction in area, i.e., final thickness of ≈0.6 mm. A micro-tensile test machine
was used for tensile tests on miniaturized samples at a constant strain rate at ambient
temperature. Tensile curves show immediately after yielding, limited uniform
elongation, and peak. This suggests that cross-slip or climb of dislocations responsible
for dynamic recovery is suppressed effectively during the deformation process. Work
hardening that is controlled by dislocation activity is limited due to high dislocation
density in these samples caused by severe plastic deformation at 77K. As the samples
were kept in the liquid nitrogen during the rolling process, the chance of dynamic
recovery is minimized and fewer grains capable of handling plastic deformation via
dislocation activity are available which results in low uniform elongation and early

9
plastic instability, as also observed in other research on ultrafine and nanocrystalline
copper.

Fig 2.1 strees strain curve for pure copper and Cu-12.1at.%Al-4.1at.%Zn

Fig 2.2 TEM micrograph of pure copper sample rolled at 77K. (a) Heavily
deformed microstructure with few ultrafine grains, (b) stack of deformation twins
in an ultrafine grain.

Fig 2.3 TEM micrograph of Cu–12.1%Al–4.1%Zn sample rolled at 77K. (a)

Heavily deformed microstructure containing twins, (b) nano twins with thickness
10
less than 10 nm.

The deformation behavior of Cu–12.1%Al–4.1%Zn is mostly controlled by dislocation

mediated processes and deformation twins do not contribute to strengthening
significantly. This is due to inhomogeneous distribution of twins in the microstructure
and large spacing of twin boundaries than the network of dislocations. Higher solute
content and reduced SFE increases yield strength. Ductility of 11% in Cu–12.1%Al–
4.1%Zn alloy is related to its tendency to form deformation twins that sustain plastic
deformation during tensile test.

[2] W.X. Qi, J.P. Tu, F. Liu, Y.Z. Yang, N.Y. Wang, H.M. Lu, X.B. Zhang, S.Y.
Guo, M.S. Liu, Microstructure and tribological behavior of a peak aged Cu-Cr-
Zr alloy (2002).

The friction and wear behavior of peak aged Cu-Cr-Zr alloys dry sliding against a brass
counter face were investigated on a pinon-disk wear tester. The microstructure of the
aged Cu-Cr-Zr alloy before and after wear tests was analyzed by transmission electron
microscopy (TEM). The sample was solution treated at 920°C for 0.5 h and water
quenched, then drawn into a rod of 5.5 mm in diameter and then it was then aged for 2
h, at 500°C, in an electric resistance furnace and subsequent air cooling was done.

Fig 2.4 TEM image obtained at the grain boundaries of the aged Cu-Cr-Zr alloy.

The peak aged Cu-Cr-Zr alloy exhibited a high Vicker hardness as a result
of dispersion of fine scale precipitate particles. Evidence from electron diffraction was
consistent with a composition of the precipitate which is most likely to be CrCu 2(Zr,
Mg).

11
[3] M. Kermajani, Sh. Raygan, K. Hanayi, H. Ghaffari, Influence of
thermomechanical treatment on microstructure and properties of electroslag
remelted Cu–Cr–Zr alloy (2013)

In this study, the effects of thermomechanical treatment on microstructure and

properties of electroslag remelted Cu–Cr–Zr Alloy were studied.

Cu–0.65Cr–0.147Zr alloy was obtained as a result of melting and refining process. The
produced ingot was extruded at 950°C with the reduction of about 400% using a
1250ton machine, solution annealed at the same temperature in an electrical furnace
and water quenched. The samples of this alloy were then 20%, 40% and 60% cold
rolled. And then those samples were aged at 500°C for 60, 90, 120, 150 and 180 minutes
using the same furnace

An optimized electroslag remelting (ESR) process was suitable to produce

homogeneous, segregation free Cu–Cr–Zr alloy with fine grained microstructure,
increased solubility of alloying elements and smaller size precipitates. The ingot was
free from undesired inclusions and other structural imperfections. The microstructural
features of the alloy after ESR like fine grains and uniform distribution of alloying
elements as a result of rapid solidification in this process.

Fine dispersed precipitates inside the grains and along the grain boundary
made the Cu–Cr–Zr alloy possess higher hardness and electrical conductivity after
aging. These particles identified to be Cu 5Zr and metallic Cr(bcc)-enriched phases.
After 40% cold working and aging for 180 min, electrical conductivity reach ed about
83% IACS. Hardness and strength values of aged samples with 60% cold working were
generally higher than those of other samples while electrical conductivity of these
samples was lower.

After performing all the combinations of thickness reduction percentages and aging
processes, optimum of mechanical properties and electrical conductivity values were
obtained after about 40% cold working and aging at 500°C for 150 min.

12
 Fig 2.5 Microstructure of alloy after ESR process.

[4] D. L. Zhang, K. Mihara, S. Tsubokawa, and H. G. Suzuki, Precipitation

characteristics of Cu–15Cr–0·15Zr in situ composite.

The ternary alloy was produced by utilization of induction melting of conditions pure
Cu (99·99%), pure Cr (99·99%), and Cu–50 wt-%Zr master alloy in a calcia crucible
under an argon atmosphere.

The in-situ Cu-15Cr-0.15Zr composite reaches peak hardness at a lower temperature

than the corresponding alloy and the Cr rich precipitates in the peak aged composite
are much smaller than those in the peak aged alloy. Precipitation free zones adjacent to
the grain boundaries of the Cu matrix are observed as common in both the alloy and
the composite. The addition of Zr enhances the precipitation hardening effect in the
alloy and the composite because of Cr rich precipitate enhances the nucleation rate and
the precipitate/matrix interfacial energy which results in increasing of the strength of
the composite.

[5] Jigar Paghadal, Kandarp Changela, Experimental study on mechanical

properties and microstructure of copper by cold and cryorolling. (2016)

Plates of Copper were subjected to rolling in four high rolling mill at cryogenic
temperature (LNT) to achieve 20% and 40% thickness reduction. The samples were
soaked in liquid nitrogen container for at least 11 min prior to each roll pass during the
rolling process and its mechanical properties and microstructure were studied.

13
 Fig 2.6 XRD test for 20% and 40%thickness for copper.

Fig 2.7 hardness chart for copper

Cryo-rolled copper exhibit a significant improvement in mechanical properties like

tensile strength and hardness compare to room temperature rolled Al alloy for 20% and
40% thickness reduction. This is because of suppression of dynamic recovery and
accumulation of higher dislocation density during lower temperature rolling resulting
in higher strength.

From optical microscope it is seen that cryorolled copper at different percent of

thickness reduction grain size number is increases when compared to room temperature
rolled sample because of work hardening and grain refinement which occur due to
higher dislocations density and network of dislocations.

[6] QIANG LIU, XIANG ZHANG, YAN GE, JING WANG, and JIAN-ZHONG

14
CUI, Effect of Processing and Heat Treatment on Behavior of Cu-Cr-Zr Alloys to
Railway Contact Wire (2006)

A new series of Cu-Cr-Zr alloys to be used as railway contact wire, a)Cu-0.26 wt %

Cr-0.15 wt % Zr, b)Cu-0.13 wt % Cr-0.41 wt % Zr, and c)Cu-0.34 wt % Cr-0.41 wt %
Zr, were studied. The results indicated that processing and aging treatment influenced
the microstructure, tensile strength, and electrical conductivity behavior of the Cu -Cr-
Zr alloys. Different processes can be considered out of which two main processes are
Process I (solution treatment + cold work + aging) and process II (cold work + solution
treatment + aging), process 1 is superior to process 2 because precipitation can occur
heterogeneously at the dislocations and sub cells. An appropriate process and aging
treatment improve the mechanical properties of the alloys due to the formation of fine,
dispersive, and coherent precipitates within the matrix.

Alloys were cast as ingots in a vacuum induction furnace. The ingots were scalped,
heated in the range of 960 °C to 980 °C for 2 hours, and then hot forged into rods of
20-mm diameter. The forged rods were first subjected to (process I) solution treated at
970 °C for 1 hour and water quenched. They were then cold drawn into rods of 6-mm
in diameter. The cold-drawn rods were then subjected to isochronal aging at
temperatures ranging from 20 (room temperature) to 800 °C for 1 hour and isothermal
aging at 480 °C for 0 to 24 hours, respectively, in an electric resistance furnace and
subsequent water quenching was done. The forged rods were in another way (process
II) cold drawn into rods of 6-mm diameter. They were solution treated at 970 °C for 1
hour and water quenched; they were then subjected to the same aging process as in
process I. Four classes of specimens were labeled, (A), (B), (C), and (D), corresponding
to the various processing and heat treatments:

(A) solution treatment 1 cold drawing 1 aging from 20 to 800 °C for 1 hour

(B) solution treatment 1 cold drawing 1 aging at 480 °C for 0 to 24 hours

(C) cold drawing 1 solution treatment 1 aging from 20 to 800 °C for 1 hour

(D) cold drawing 1 solution treatment 1 aging at 480 °C for 0 to 24 hours

Solution heating temperature plays an important role in strengthening the Cu-Cr-Zr

alloys. The best solution heating temperature is in the range of 960°C to 980°C.

Tensile strength and electrical conductivity increased after aging was done to the
samples. The best combination of strength and electrical conductivity (530 MPa, 78 %

15
IACS) was achieved after aging at 480°C for 1 hour. The increase in strength and
electrical conductivity is due to precipitation of Cr particles during the aging treatment.
With an increase in strength on aging, there is also an increase in electrical conductivity.

The strengthening efficacy of process I is much higher than that of process II, and the
peak aging time is shorter than process II. This behavior appears to be due to the
enhanced kinetics of precipitation as a result of cold drawing. The content of additives
influences the strength of the alloys to some extent. Specimen C has the highest strength
in this study.

[7] T. Konkova, S. Mironov, A. Korznikov, S.L. Semiatin, Microstructural

response of pure copper to cryogenic rolling. (2010)

Copper of 99.9 wt.%. purity which was received in the form of hot-rolled bar, cryogenic
rolling was conducted on specimens that were cut perpendicular to the final
compression axis from the central, most severely deformed part of the SPDed billets.
The specimens were rolled to 50%, 75% or 93% overall thickness reductions (true
strains of 0.7, 1.4 and 2.7) using a cluster mill with 65 mm of roll diameter. The total
thickness reductions were achieved using multiple passes of 10% each. In order to
provide cryogenic deformation conditions, both the rolling specimen and the rolls were
soaked in liquid nitrogen 20minutes prior to each pass and immediately after each pass,
the workpiece was reinserted into liquid nitrogen.

The EBSD technique has been employed to establish the microstructural response of
pure copper to cryogenic rolling and to evaluate the potential of this approach to
produce NC (nano crystalline) materials.

The results from this work obtained are

a) Not appreciable contribution from grain subdivision and twinning in grain

refinement.

b) Recrystallization probably takes place after cryogenic deformation during static

storage of rolled material at room temperature and also it is discontinuous in nature

c) As cross-slip gets suppressed at cryogenic temperatures this effect is likely

responsible for the limited formation of well-defined sub grains during deformation.

d) Cryogenic deformation significantly reduces the mean grain size but a desirable NC-
range is not achieved by this process. Grain-refinement is mainly associated with
16
recrystallization and is probably a post-deformation effect and the incorporation of
second-phase particles in copper alloys may retard recrystallization following
cryogenic deformation and give rise to an NC microstructure.

[8] S. Nagarjuna∗, U. Chinta Babu, Partha Ghosal, Effect of cryo-rolling on age

hardening of Cu–1.5Ti alloy. (2008)

A Cu–1.5Ti alloy was prepared with the help of vacuum induction melting (VIM)
furnace and cast in a graphite mould. The ingot was homogenized at 750 °C for 24 h
and analyzed for its composition. And it results in Cu-1.48%Ti. The ingot was
subsequently hot forged and rolled after soaking at 800°C to obtain 10 mm thick flats
and rods of 12 mm in diameter.

Table 2.1 comparison of mechanical properties of cryorolled Cu-1.5%Ti and RT

rolled Cu-1.5%Ti alloy

Cryo-rolling results in two peaks in hardness during aging of Cu–1.5Ti alloy. The aging
got accelerated as peak aging temperature and time got decreased significantly to 400°C
and 4 h respectively as against 450°C and 16 h for the as-quenched Cu–1.5Ti alloy due
to increased dislocation density.

A maximum hardness of 300 H v, YS of 824 MPa and UTS of 854 MPa are obtained on
90% deformation at liquid nitrogen temperature and peak aging at 400°C which are
considerably higher than that cold rolled at room temperature (RT) and peak aged as
rolling at LNT results in extremely high dislocation density, which in turn has nucleated
still higher density of precipitates during aging leading to higher strength properties
over that rolled at RT and peak aged sample.

The ductility decreased significantly in cryo-rolled and peak aged alloy and reaches a
lowest value of 4% elongation. The predominant strengthening mechanism is the
precipitation of an ordered, metastable and coherent β-Cu 4Ti phase during aging in
17
addition to deformation twins and dislocation cells.

The over aging is associated with the formation of coarse discontinuous precipitates of
equilibrium phase Cu 3Ti thus, results in decreasing of hardness and strength.
Recrystallisation leading to formation of fine grains has not been observed in the cryo-
rolled Cu–1.5Ti alloy aged at 400°C or even at 500°C.

[9] I. S BATRA, G.K.DEY, U.D. KULKARNI, S. BANERJEE, microstructure and

properties of Cu-Cr-Zr alloy. (2001)

In this study they have taken Cu-0.8Cr-0.08Zr alloy is used in the heat transfer element
in an aged condition. Aging was carried out on this sample just below 1000 °C and
CTEM (conventional transmission electron microscope) microstructures are taken for
analysis and in that twinning found to be more predominant than gradually slip nature
of pure copper this leads to lowering of SFE on addition of Zr to dilute copper-
chromium alloy. Lowering of SFE leads to dissociation of screw dislocations into their
partials making cross glide difficult and then twinning becomes easy and extensive.

Fig 2.8 Light micrograph of solutionized plus aged alloy

Fig 2.9 DF micrograph showing a large chromium particle

18
In this study two kinds of second phase particles were observed, coarse chromium
particles formed during solidification and left undissolved during solutionizing. From
decomposition of the solid solution the precipitates of ordered bcc chromium.

Decomposition sequence is as follows: supersaturated solid solution -solute rich

clusters-metastable ordered fcc ordered phase-ordered bcc precipitates. On lowering of
SFE due to addition of Zr the fatigue properties got improved.

[10] Ping LIU, Juanhua SU, Qiming DONG and Hejun LI, Microstructure and
Properties of Cu-Cr-Zr Alloy after Rapidly Solidified Aging and Solid Solution
Aging. (2004)

Cu-0.3Cr-0.15Zr alloy ingot was made from induction-melted in a quartz tube and then
jetted under the pressure of pure Ar to a Cu roller rotating at a speed of about 1200
revolutions/min. The strengthening effect in conventional solid solution aging is limited
due to low solubility of Cr in Cu at the solid solution temperature, and coarse grain
structure. Rapid solidification, e.g. melt spinning, can leads to extension of the solid
solubility of Cr and Zr in Cu matrix and remarkable refinement of grain size.

Fig 2.10 Hardness vs aging time and temperature of (a)SSA (b) RSA.

The microstructure and grain size after rapid solidification are much more uniform and
smaller than that after solid solution, which is the reason for the increase in hardness of
Cu-Cr-Zr alloy and also more fine dispersed precipitates inside the grains and along the
grain boundary make the Cu-Cr-Zr lead frame alloy possess higher hardness.

Rapidly solidified aging processes can greatly enhance the hardness and electrical
conductivity for Cu-Cr-Zr alloy, specifically at the early stage of aging. After aging at
500°C for 15 min the hardness of the alloy is 143 H v and the conductivity can reach
19
72% IACS whereas for solid solution under the same aging condition, the hardness and
electrical conductivity can reach 86 H v and 47% IACS, respectively.

[11] J.H. Su, P. Liu, Q.M. Dong, H.J. Li, F.Z. Ren, and B.H. Tian, Recrystallization
and Precipitation Behavior of Cu-Cr-Zr Alloy. (2006)

Cu-0.7Cr-0.13Zr was prepared by solution treatment for 1 h at 920°C in an argon(Ar)

atmosphere and water quenching the samples subsequently rolling was carried up to
extent of deformation that was prefixed to perform. Three processes are performed,

1. Cold rolled up to 80% thickness reduction.

2. Cold rolled up to 80% thickness reduction and aged for 1hr at 500°C.

3. Cold rolled up to 80% thickness reduction and aged for 6hrs at 600°C.

The results obtained from Vickers hardness test and SEM analysis are as follows:

Fig 2.11 Hardness with regard to time aged at 500°C

Fig 2.12 Hardness with regards to strain aged for 2h

20
Fig 2.13 Scanning electron micrographs showing the microstructures of Cu-
0.76Cr-0.13Zr alloy after being: (a) predeformed by 80% cold rolling, (b)
predeformed by 80% and aged for 1 h at 500°C, (c) predeformed by 80% and aged
for 4 h at 600°C.

Upon aging, the precipitation process takes place prior to recrystallization for the cold-
deformed Cu-Cr-Zr alloy. The pinning of the dispersed fine precipitates on dislocation
has shown a restraining effect on the following recrystallization process. With 80%
rolled and aged at 450°C for 2 h, the hardness of the alloy is 180.3HV.

The heavily deformed and aged at high-temperature alloy showed coarser precipitate
particles and an accelerated process of recrystallization rolled to 80% and aged at 600°C
for 2 h, the hardness reduces to 136H V which is the highest value of hardness achieved
in this process.

[12] Ryota Ihira, Hyoseong Gwon, Ryuta Kasada∗, Satoshi Konishi, Improvement
of tensile properties of pure Cu and Cu-Cr-Zr alloy by cryo-rolling process. (2016)

Precipitation-hardened Cu-Cr-Zr alloy will be used for the cooling tube of tungsten
mono-block divertor of ITER because of its excellent strength, thermal conductivity. A
25 mm rod of commercial grade Cu-1.0Cr-0.1Zr alloy was cut into a disk of 10 mm
thickness and solutionized at 980°C for 30 min. Cryorolling of the solutionized sample
was performed immediately after immersing the samples in liquid nitrogen. Cryorolling
process was repeated and many number of passes are required so as to achieve 93%
21
thickness reduction and then precipitation heat treatment was carried out by ageing at
475°C for 3 h. In the same way, Conventional cold-rolling and without rolling aging
was done to compare the mechanical properties with the cryorolled sample.

In the same way, the three operations are carried out but at aging temperature of 200°C
for 20minutes for analysis.

Fig 2.14 Engineering stress–strain curves of (a) pure copper and (b) CuCrZr alloy.

Cryo-rolled CuCrZr alloy showed an increase of strength without loss-of-ductility

compared with conventional cold-rolled CuCrZr alloy. This benefit of cryo-rolling
process was attributed to the temperature transition of texture formation to have brass
and Goss orientation which are effective for tensile deformation along rolling direction.

[13] Mediha Ipek, CHARACTERIZATION OF AN Cu-Cr-Zr ALLOY

SYNTHESIZED WITH THE POWDER-METALLURGY TECHNIQUE. (2014)

Cu-1.5 % Cr-0.5 % Zr alloy was prepared under powder metallurgy route. After
completion of sintering of powder samples, solution treatment is done at 1000°C for
15minutes and immediately water quenched the samples later they were mechanically
deformed by 20 % at room temperature. Aging was carried out at 470 °C for
2h,4h,6h,8h as time periods.

Phase analysis of the as-sintered, solution-treated, water-quenched and aged samples

was carried out with the XRD-analysis technique using the Cu-Kα radiation. The
microstructures of the products were examined by means of scanning electron
microscopy, energy dispersive spectroscopy (SEM-EDS).

22
Fig 2.15 SEM micrographs of the samples: a) as sintered, b) sintered, solution-
treated, quenched and aged for 8

Fig 2.16 XRD patterns of the sinter-pressed sample and the sintered, solution-
treated, quenched and aged samples

cold deformation enhances the relative density of the as sintered samples; cold
deformation and aging increase the hardness and electrical conductivity from 77 H V to 116
HV, and from 76 % IACS to 87 % IACS, respectively.

[14] Shaojian Zhanga, Rengeng Lia, Huijun Kangb, Zongning Chenb, Wei Wanga ,
Cunlei Zoua , Tingju Lib , Tongmin Wanga, A high strength and high electrical
conductivity Cu-Cr-Zr alloy fabricated by cryorolling and intermediate aging
treatment. (2017)

Besides SPD processes, cryorolling, i.e., rolling at liquid nitrogen temperature (LNT) has
been attempted on several metals and alloys to obtain ultrafine grained materials with high
density of dislocations for improving mechanical properties.

A test material with a nominal composition of Cu-1 wt%Cr-0.1 wt% Zr alloy was prepared
by using electrolytic copper (purity of 99.99%), pure chrome (purity of 99.99%) and Cu-
49.9%Zr master alloy in a vacuum induction furnace under argon atmosphere, and casted
23
in a metal mold. Solution treatment at 960°C for 1 h prior to water quenching.

Table 2.2 rolling-aging routes

Fig 2.17 Bright field TEM Images showing deformation twins and Cr precipitates
(heat treatment)

24
Fig 2.18 tensile test and electrical conductivity results

Desired combination of tensile strength (690.13 MPa) and electrical conductivity (67%
IACS) can be obtained for the alloy after primary 30% cryorolling and aging at 450 °C for
2 h followed by secondary 60% cryorolling.

The improved strength of the Cu-Cr-Zr alloy is attributed to the interactions of TBs
strengthening, GBs strengthening, precipitation strengthening and strain hardening during
deformation and aging treatment.

25
 CHAPTER 3
OBJECTIVES

The objectives of this study are as following:

• Microstructure and phase analysis of both cryorolled and cold-rolled samples by

using optical microscope and X-Ray Diffraction
• Identification of deformation twins and precipitates by TEM images
• Determination of strength and hardness from tensile test and hardness test.

26
 CHAPTER 4
WORKPLAN

Step 1: literature review

Step 2: Sample preparation of Cu-Cr alloy for rolling
Step 3: Solution treatment at 960°C for 15 minutes.
Step 4: a. cold rolling of sample up to 70% thickness reduction
b. cold rolling of sample up to 70% thickness reduction + aging at 450°C
for 2hrs
c. cold rolling of sample up to 35% thickness reduction + aging at 450°C
for 2hrs + cold rolling of sample up to 35% thickness reduction
d. cryorolling of sample up to 70% thickness reduction
e. cryorolling of sample up to 70% thickness reduction + aging at 450°C
for 2hrs
f. cryorolling of sample up to 35% thickness reduction + aging at 450°C
for 2hrs + cryorolling of sample up to 35% thickness reduction.
Step 5: micro tensile test, micro-Vickers hardness test, TEM, XRD, optical
microscopy.
Step 6: Data analysis and report making.

27
 CHAPTER 5
REFERENCES

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Materials Science & Engineering A 680 (2017) 108–114.

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Effect of cryogenic rolling and annealing on the microstructure evolution and
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characteristics of Cu–15Cr–0.15Zr in situ composite.

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29