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Surface Engineering Notes 1
Surface Engineering Notes 1
FACULTY OF ENGINEERING
Mechanical & Production Engineering Department
Manufacturing Processes & Metrology - MECH 3002Y
SURFACE ENGINEERING NOTES
General Introduction
SURFACE ENGINEERING is a multidisciplinary activity intended to tailor the properties of the
surfaces of engineering components so that their function and serviceability are improved.
Surface Engineering can be defined as treatment of the surface engineering as treatment of the
surface and near-surface regions of a material to allow the surface to perform functions that are
distinct from those functions demanded from the bulk of the material. Of concern to the design
engineer is the availability of surface-specific properties for the component that can provide:
Of further concern to the designer is the availability of economical processes to produce the
required properties. These processes include solidification treatments such as hot dip coatings,
weld-overlay coatings, and thermal spray surfaces; deposition surface treatments such as
electrodeposition, chemical vapor deposition, and physical vapor deposition, and heat treatment
coatings such as diffusion coatings and surface hardening.
Surface treatments are used in a variety of ways to improve the material properties of the
component. Coating mechanical properties, for example, hardness, strength, and toughness, can
improve the component wear, fatigue, and erosion properties, respectively. Electrical properties
in circuit design are dependent on the surface-deposition processes. Similarly, environment
properties, such as resistance to aqueous corrosion and high-temperature oxidation and
sulfidation, can be improved by selective surface treatments.
Although the surface normally cannot be made totally independent from the bulk, the demands
on surface and bulk properties are often quite different. For example, in the case of a turbine
blade for a high-performance jet engine, the bulk of the material must have sufficient creep
resistance and fatigue strength at the service temperature to provide an acceptably safe service
life. The surface of the material, conversely, must possess sufficient resistance to oxidation and
hot corrosion under the conditions of service to achieve that same component life. In many
instances, it is either more economical or absolutely necessary to select a material with the
required bulk properties and specifically engineer the surface to create the required interface with
the environment, rather than to find one material that has both the bulk and surface properties
required to do the job.
SURFACE CLEANING
Cleaning Process Selection
IN SELECTING A METAL CLEANING PROCESS, many factors must be considered,
including
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(l)
Types of soil can be broadly classified into six groups; pigmented drawing compounds,
unpigmented oil and grease, chips and cutting fluids, polishing and buffing compounds, rust and
scale, and miscellaneous surface contaminants, such as lapping compounds and residue from
magnetic particle inspection.
Removal of Rust and Scale
The seven basic methods used for removing rust and scale from ferrous mill products, forgings,
castings, and fabricated metal parts are:
The most important considerations in selecting one of the previous methods are:
Alkaline Cleaning
ALKALINE CLEANING is a commonly used method for removing a wide variety of soils from
the surface of metals. Soils removed by alkaline cleaning include oils, grease, waxes, metallic
fines, and dirt. Alkaline cleaners are applied by either spray or immersion facilities and are
usually followed by a warm water rinse. A properly cleaned metal surface optimizes the
performance of a coating that is subsequently applied by conversion coating, electroplating,
painting, or other operations. The main chemical methods of soil removal by an alkaline cleaner
are saponification, displacement, emulsification and dispersion and metal oxide dissolution.
Alkaline Cleaner Composition
Alkaline cleaners have three major types of components; builders, which make up the bulk of the
cleaner; organic or inorganic additives, which promote better cleaning or affect the rate of metal
oxide dissolution of the surface, and surfactants.
Builders are the alkaline salts in an alkaline cleaner. Most cleaners use a blend of different salts:
The corresponding (and more expensive) potassium versions of these salts are also commonly
used, especially in liquid cleaner formulations. The choice of salts for a given cleaner is based
on the metal being cleaned, the cleaning method, performance requirements, and economics.
Table 2 shows a few common formulations for specific combinations of metal and cleaning
methods.
Phosphates are of great importance in the builder packages of alkaline cleaners. A key function
of phosphates is their ability to complex with hard water salts. By softening these hard water
salts, they eliminate the formation of flocculate precipitation caused by calcium, magnesium and
iron. Phosphates are also effective as dispersants for many types of soils. Additionally, they
provide alkalinity and prevent large changes in the pH of the cleaning solution.
Sillicates are an expensive source of alkalinity and buffering. They are useful in powdered
cleaners as adsorbents for liquid components. hydroxides are relatively inexpensive and are the
strongest form of alkalanity available.
Borates provide strong buffering at a moderately alkaline pH. They have been used extensively
in the cleaning of aluminum. Borates provide a degree of metal inhibition and aid detergency.
Additives are organic or inorganic compounds that enhance cleaning or surface modification.
Chemical compounds such as glycols, glycol ethers, corrosion inhibitors and chelating agents
should be considered additives. Some widely used chelating agents are sodium gluconate,
sodium citrate, tetrasodium ethylenerliamine tetraacetic acid (EDTA), trisodium nitrilotriacetic
acid (NTA), and triethanolamine (TEA).
Surfactants are organic and are the workhorses of alkaline cleaners. They are key in displacing,
emulsifying, and dispersing many of the soils found on a metal surface. Surfactants lower the
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surface tension of the cleaner at the metal surface, allowing it to cover the surface uniformly.
There are found major types:
Vapor Degreasing
Vapor degreasing is a generic term applied to a cleaning process that uses the hot vapors of a
chlorinated or fluorinated solvent to remove soils, particularly oils, greases, and waxes. A vapor
degreasing unit consists of an open steel tank with a heated solvent reservoir, or sump, at the
bottom and a cooling zone near the top. Sufficient heat is introduced into the sump to boil the
solvent and generate hot solvent vapor. Because the hot vapor is heavier than air, it displaces the
air and fills the tank up to the cooling zone. The hot vapor is condensed when it reaches the
cooling zone, thus maintaining a fixed vapor level and creating a thermal balance. The
temperature differential between the hot vapor and the cool workpiece causes the vapor to
condense on the workpiece and dissolve the soil.
Ultrasonic Cleaning
ULTRASONIC CLEANING involves the use of high-frequency sound waves (above the upper
range of human hearing, or about 18 kHz) to remove a variety of contaminants from parts
immersed in aqueous media. The contaminants can be dirt, oil, grease, buffing/polishing
compounds, and mold release agents, just to name a few. Materials that can be cleaned include
metals, glass, ceramics, and so on. Ultrasonic agitation can be used with a variety of cleaning
agents; detailed information about these agents is available in the other sections on surface
cleaning.
Typical applications found in the metals industry are removing chips and cutting oils from
cutting and machining operations, removing buffing and polishing compounds prior to plating
operations, and cleaning greases and sludge from rebuilt components for automotive and aircraft
applications.
Ultrasonic cleaning is powerful enough to remove tough contaminants, yet gentle enough not to
damage the substrate. It provides excellent penetration and cleaning in the smallest crevices and
between tightly spaced parts in a cleaning tank.
The use of ultrasonics in cleaning has become increasingly popular due to the restrictions on the
use of chlorofluorocarbons such as 1,1,1-trichloroethane. Because of these restrictions, many
manufacturers and surface treaters are now using immersion cleaning technologies rather than
solvent-base vapor degreasing. The use of ultrasonics enables the cleaning of intricately shaped
parts with an effectiveness that corresponds to that achieved by vapor degreasing.
in the use of these terms occurs. Acid pickling is a more severe treatment for removal of scale
from semi-finished mill products forgings, or castings, whereas acid cleaning generally refers to
the use of acidic solutions for final or near-final preparation of steel surfaces before plating,
painting, or storage.
Abrasive Blast Cleaning
ABRASIVE BLAST CLEANING entails the forceful direction of abrasive particles, either dry
or suspended in a liquid, against the surfaces of parts to products. Abrasive blast cleaning
removes contaminants and conditions the surfaces for subsequent finishing. Typical uses
include:
Removing rust, scale, dry solids, mold sand, ceramic shell coatings, or dried paint.
Roughening surfaces in preparation for bonding, painting, enameling, or other coating
substances.
Removing large burrs or weld spatter.
Developing flash from rubber or plastic molding operations.
Carving of decorative etching of glass, porcelain, wood or natural stone such as granite
or marble.
Abrasive for Dry Blast Cleaning
The materials used in dry abrasive blast cleaning can be categorized as metallic grit, metallic
shot, sand, glass, and miscellaneous. Hardness density, size and shape are important
consideration in choosing an abrasive for a specific application.
Electropolishing
ELECTROPOLISHING is a nonabrasive electrochemical process for removing metal. Etching,
deburring, smoothing, coloring and machining are typical electropolishing processes. The
removal of metal is done anodically in acid and alkaline solutions.
During the process, products of anodic metal dissolution react with the electrolyte to form a film
at the metal surface. Two types of films have been observed:
(a) a viscous liquid that is nearly saturated, or is supersaturated, with the dissolution
products, and
(b) anodically discharged gas, usually oxygen. Both types of films exist simultaneously in
most commercial electropolishing solutions. The gas appears to be a blanket on the
outside of the viscous film. Which type of film predominates depends on (a) the kind of
metal, (b) the nature of the electrolyte, and (c) the surface condition prior to
electropolishing (i.e surface contamination, grain size, and inclusions).
Mass Finishing
MASS FINISHING normally involves loading of components to be finished into a container
together with some abrasive medium, water and compound. Action is applied to be the container
to cause the medium to rub against the surfaces, edges and corners of the components, or to
cause the components to rub against each other, or both. This action may deburr, generate edge
and corner radii, clean the parts by removing rust and scale, and modify the surface stress. The
basic mass finishing processes include:
Barrel finishing
Vibratory finishing
Centrifugal disk finishing
Centrifugal barrel finishing
Spindle finishing
Barrel Finishing
The rotary barrel, or tumbling barrel, utilizers the sliding movement of an upper layer of
workload in a barrel. The barrel is normally loaded about 60% full with a mixture of parts,
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medium, compound, and water. As the barrel rotates, the load moves upward to a turnover
point; then the force of gravity overcomes the tendency of the mass to stick together, and the top
layer slides toward the lower area of the barrel.
Vibratory Finishing
A vibratory finishing machine is an open-topped tub or bowl mounted on springs, usually lined
with polyurethane. Parts and medium are loaded in a fashion similar to that of a tumbling barrel.
With a vibratory machine, the container can be almost completely filled. Vibratory action is
created by a vibratory motor attached to the bottom of the container, by a shaft or shafts with
eccentric loads driven by a standard motor, or by a system of electromagnets operating at 50 or
60 Hz. The action of the medium against the components takes place throughout the load, so
that process cycles are substantially shorter than those of conventional tumbling in barrels.
Shot Peening
SHOT PEENING is a method of cold working in which compressive stresses are induced in the
exposed surface layers of metallic parts by the impingement of a stream of shot, directed at the
metal surface at high velocity under controlled conditions. It differs from blast cleaning in
primary purpose and in the extent to which it is controlled to yield accurate and reproducible
results. Although shot peening cleans the surface being peened, this function is incidental. The
major purpose of shot peening is to increase fatigue strength. The process has other useful
applications, such as relieving tensile stresses that contribute to stress-corrosion cracking,
forming and straightening of metal parts, and testing the adhesion of silver-place on steel.
Types of Sizes of Media
Media used for peening include:
Cast steel shot, which is the most widely used medium, produced in two hardness ranges:
40 to 50 HRC and 57 to 62 HRC.
Cast iron shot with an as-cast hardness of 58 to 65 HRC.
Glass beads with a hardness equivalent to 46 to 50 HRC
Cut carbon or stainless steel wire.
Metallic shot is designated by numbers according to size. Shot numbers, as standardized by
MIL-S-13165, range from S70 to S930. The shot number is approximately the same as the
nominal diameter of the individual pellets in ten thousandths of an inch. Glass shot, used
primarily for peening nonferrous material, is available in a wider range of basic diameters.
Equipment
The equipment used in shot peening is essentially the same as that used in abrasive blast,
cleaning, except for certain auxiliary equipment made necessary by the more stringent controls
imposed in the shot peening process. The principal components of shot peening equipment are a
shot-propelling device, shot recycling and classification arrangements, and a work handling
conveyor. All portions of equipment that are exposed to the stream of shot are enclosed to
confine the shot and permit it to be recycled.
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Manganese phosphate coatings are applied to ferrous parts (bearing, gears, and internal
combustion engine parts, for example) for break in and for prevention of galling. These coatings
are usually dark gray. However, because almost all manganese phosphate coatings are used as
an oil base and because the oil intensifies the coloring, manganese phosphate coatings are
usually black in appearance.
Porcelain Enameling
PORCELAIN ENAMELS are glass coatings applied primarily to products made of steel sheet,
cast iron, or aluminum to improve appearance and protect the metal surface. Porcelain enamels
are distinguished from other ceramic coatings by their predominantly vitreous nature and the
types of applications for which they are used, and from paint by their inorganic composition and
the fusion of the coating matrix to be substrate metal. Porcelain enamels of all compositions are
matured at 425C or above.
Types of Porcelain Enamels
Porcelain enamels for steel sheet and cast iron are classified as either ground-coat or cover-coat
enamels. Ground-coat enamels contain oxides that promote adherence of the enamel to the metal
substrate. Cover-coat enamels are applied over ground coats to improve the appearance and
properties of the coating.
The basic material of the porcelain enamel coating is called a frit; it is a special glass of small
friable particles produced by quenching a molten glassy mixture. Because porcelain enamels are
usually designed for specific applications, the compositions of the frits from whcih they are
made vary widely.
Enamel Frits for Steel Sheet. All the frits fro which compositions are given in Table 8 are
classified as alkali borosilicates for use as ground coats on steel sheet. Their compositions differ
depending on the application environment of the enameled product.
Cover costs for steel sheet are applied over ground coats or directly to properly prepared
decarburized steel. Compositions of frits for cover-coat enamels are given in Table 9.
Electrostatic dry-powder cover coats can be applied over an electrostatic dry-powder ground coat
and the entire two-coat/one-fire system matured in a single firing.
Enamel Frits for Cast Iron. Composition of frits for enamels for cast iron vary depending on
whether the frit is applied by the dry process or the wet process. Dry-process enamels are
commonly used for large cast iron fixtures because of their brilliance and ability to cover small
surface irregularities.
Enamel Frits for Aluminum are usually based on lead silicate and on cadmium silicate, but can
be based on phosphate or barium.
The high-lead enamels for aluminum have a high loss, good acid, and weather resistance, and
good mechanical properties.
Chemical Vapor Deposition and Related Processes
CHEMICAL VAPOR DEPOSITION (CVD) involves the formation of a coating by the reaction
of the coating substance with the substrate. The coating species can come from a gas or gases or
from contact with a solid as in the pack cementation process. The process is more precisely
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defined as the deposition of a solid on a heated surface by a chemical reaction from the vapor or
gas phase. In general, three processing steps are involved in any CVD reaction:
(1) the production of a volatile carrier compound
(2) the transport of the gas to the deposition site without decomposition and
(3) the chemical reaction necessary to produce the coating on the substrate.
The numerous chemical reactions used in CVD include thermal decomposition (pyrolysis),
reduction, hydrolysis, disproportionation, oxidation, carburzation and nitridation. These
reactions take place singly or in combination and are controlled by thermodynamics; kinetics;
mass transport; chemical of the reaction; and processing parameters of temperature, pressure, and
chemical activity.
CVD Processes
Chemical vapor deposition processes can be classified as either open-reactor systems, including
thermal CVD and plasma CVD, or as a closed-reactor system, as in pack cementation. In
thermal CVD, reactions usually take place above 900C, whereas plasma CVD usually operates
at temperature between 300 and 700C (Table 1). Using the lower reaction temperature plasma
CVD enables coatings to be produced on substrates with low melting points or that otherwise
would undergo solid state transformations over the range of deposition temperature.
Furthermore, the low deposition temperature of plasma CVD coatings limits the stresses due to
the large mismatches in thermal expansion that can lead to cracking and determination of the
coating.
selectively removes graphite and activates and stablizes the diamond structure. The basic
reaction involves the decomposition of methane, which can be activated by microwave plasma,
thermal means (hot filament), plasma arc, or laser.
Material
Thermal CVD
C
Plasma CVD
C
Silicon nitride
900
1650
300
570
Silicon dioxide
800 - 1100
1470 - 2010
300
570
Titanium carbide
900 - 1100
1650 - 2010
500
500
Titanium nitride
900 1100
1650 - 2010
500
500
Tungsten carbide
1000
1830
325 - 525
615 - 975
used for the same type of applications as chromium electroplate. Physical vapor deposition
coatings have hardnesses greater than any metal and are used systems that cannot tolerate even
microscopic wear losses. Most processes are operated on a batch basis, and the component size
is limited by the size of the vacuum chamber. Provided that the substrate can be manipulated to
face the coating source, the size and shape of objects are limited by the capital and operating
expenditures involved rather than by the fundamental characteristics of the process.
Furthermore, cleanliness of the substrate is critical and far exceeds, surface preparation
requirements for other coatings.
Sputtering
Process Description. Sputtering is the principal PVD process. It involves the transport of a
material from a source (target) to a substrate by means of the bombardment of the target by gas
ions that have been accelerated by a high voltage. Atoms from the target are ejected by
momentum transfer between the incident ions and the target. These ejected particles move
across the vacuum chamber to be deposited on the substrate.
In its simplest form, the process occurs in an inert (noble) gas at low pressure 0.13 to 13 Pa, or 1
x 10-3 to 100 x 10-3 torr); in most cases, the gas is argon because it has a higher mass than neon
or helium; higher mass gives a higher sputtering yield.
The sputtering process begins when an electric discharge is produced and the argon becomes
ionized. The low-pressure electric discharge is known as glow discharge, and the ionized gas is
termed plasma.
The argon ions hit the solid target, which is the source of the coating material (and not to be
confused with the substrate, which is the item to be coated). The target is negatively biased and
therefore attracts the positively charged argon ions, which are accelerated in the glow discharge.
This attraction of the ions to the target (also known as bombardment) causes the target to sputter,
which means that material is dislodged from the target surface because of momentum energy
exchange. The higher the energy of the bombarding ions, the higher rate of material
dislodgement.
Application. The materials that can be sputter coated are pure metals, alloys, inorganic
compounds, and some polymeric materials. A major restriction to be considered for the
substrate material is the temperature of the process, which can range from 260 to 540C.
Sputtering is often used for depositing compounds; and materials that are difficult to coat by
thermal evaporation techniques. Engineering applications of sputter coatings include:
substrate. Some evaporant atoms pass through the plasma in atomic for, while some atoms
collide with electrons from the substrate and become ions. They impinge on the substrate in
ionic form, pick up electrons, and return to the atomic state, forming the coating. Figure 5 shows
a schematic of the ion plating process with a resistance heated vaporization source. Electron
beam evaporation is also used.
A variant process is reactive ion plating in which the metallic constituent (titanium) of the
compound (titanium nitride, TiN) is evaporated into the reactive gas mixture of argon and
nitrogen that is enhanced by the glow discharge, depositing a golden colored TiN coating on the
substrate. Films of TiN are applied to a wide range of tools, such as bits, punches, dies, and taps
to improve tool life by three to ten times. Figure 4 shows the improvement in abrasion resistance
of reactive ion plating over other PVD sputtering processes. The results show that the higher
energy reactive ion plating process had more then an order of magnitude improvement over the
radio-frequency diode sputtered coatings.
Applications. In addition to the TiN-coated tools mentioned previously, other typical
applications of the ion plating process include:
Good adhesion between a film and substrate (for example, silver on steel for mirrors,
silver on beryllium for diffusion bonding).
Electrical conductive layers (aluminum, silver and gold) on plastics and
semiconductors.
Low-shear solid film lubricants (for example silver and gold)
Decorative coatings (TiN yields gold-colored deposit, TiCxNy yields rose-colored
deposit, TiC yields, black deposit, zirconium nitride, ZrN, yields brass-colored deposit)
applied to hardware, jewelry, guns and cutlery.
Corrosion protection: aluminum on uranium, steel (replacing cadmium) and titanium;
and carbon and tantalum on biological implants.
Deposition of electrically conductive diffusion barriers (for example, hafnium nitride,
HfN, and TiN on semiconductor devices).
Ion Implantation
Process Description. Ion implantation involves the bombardment of a solid material with
medium-to-high-energy ionized atoms and offers the ability to alloy virtually any elemental
species into the near surface region of any substrate. The advantage of such a process is that it
produces improved surface properties without the limitations of dimensional changes or
delaminating found in conventional coatings. During implantation, ions come to rest beneath the
surface in less than 10 to 12 s, producing a very fast quench rate and allowing the development
of nonequilibrium surface alloys or compounds. Disadvantages of the process include shallow
penetration depths (on the order of a few hundred angstroms) and relatively high capital and
operating costs. Ion implantation is commercially applied to various steels, tungsten,
carbide/cobalt materials, and alloys of titanium, nickel, cobalt, aluminum, and chromium,
although applications are restricted to temperatures below 250C for steels and 450C for
carbides.
Table 2 lists some of the applications for the ion-implantation process. Ion-implantation surfaces
produce exceptional results in reducing wear, friction, and corrosion. Commercial applications
involve tooling, bearings, and biomedical components. Nitrogen implantation has been
especially successful in increasing the life (up to 20 times) of tools and parts used in the
manufacture of injection-molded plastics. Titanium and cobalt chromium alloy orthopedic
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prostheses for hip and knee joints are among the most successful commercial applications for
ion-implantation components for wear resistance.
Table 2 - Research and development applications for ion implantation
Surface properties Substrates studied
Ions species used
Comments
modified
Wear
Steels, WC Ti,
N, C
Ti,
Co/Cr
alloys
Co/Cr alloys, TiN 10-20 at, %
largest
use
17
2
coatings,
commercially
in
10 ions/cm
Electroplated Cr
orthopedic devices
Friction
Steels
Ti plus C implants
Dual implants give
17
2
amorphous
surface
10 ions/cm
layer
Fatigue
Ti alloys, steels
N, C
Implantation effective
for surface initiated
1017 ions/cm2
fatigue
Fracture toughness
Ceramics: Al2O3
Ar
Radiation
damage
15
17
2
TiN
10 10 ions/cm
critical; ion-induced
compressive
stress
helpful
Aqueous
corrosion Steels, Ti alloys, Pt
Cr, Ta, Cr + P
Ion implant can mimic
17
2
catalysis
normal alloys;
10 ions/cm
amorphous
and
unique surface alloys
possible
Oxidation
Superalloys
Y, Ce
Low effective doses;
implanted species stay
1015 ions/cm2
at
metal-oxide
interface
Electrical
Polymers
Ar, F
Permits
chain
15
17
2
conductivity
scissoning,
doping;
10 10 ions/cm
conductivity
approaches disordered
metal level
Optical:
refractive Glasses, electrooptics Li, Ar
Chemical doping and
15
17
2
index
lattice disorder both
10 10 ions/cm
important
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