UNIVERSITY OF MAURITIUS

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:

• Protection in a desired environment

• Improved mechanical properties
• Electronic or electrical properties
• Desired appearance

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.

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SURFACE CLEANING

Cleaning Process Selection

IN SELECTING A METAL CLEANING PROCESS, many factors must be considered,

including

(a) the nature of the soil to be removed

(b) the substrate to be cleaned (ie. ferrous, nonferrous, etc)
(c) the importance of the condition of the surface to the end use of the part
(d) the degree of cleanliness required
(e) the existing capabilities of available facilities
(f) the environmental impact of the cleaning process
(g) cost considerations
(h) the total surface area to be cleaned
(i) effects of previous processes
(j) rust inhibition requirements
(k) materials handling factors
(l) surface requirements of subsequent operations, such as phosphate conversion coating,
painting or plating.

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:

• Abrasive blasting (dry or wet)

• Tumbling (dry or wet)
• Brushing
• Acid pickling
• Salt bath descaling
• Alkaline descaling
• Acid cleaning

The most important considerations in selecting one of the previous methods are:

• Thickness of rust or scale

• Composition of metal
• Condition of metal (product form or heat treatment)
• Allowable metal loss
• Surface finish tolerances
• Shape and size of work pieces
• Production requirements
• Available equipment
• Cost
• Freedom from hydrogen embrittlement

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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:

• Orthophosphates, such as trisodium phosphate

• Condensed phosphates, such as sodium pyrophosphate and sodium tripolyphosphate
• Sodium hydroxide
• Sodium metasilicate
• Sodium carbonate
• Sodium borate

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:

• Anionic (e.g. sodium alkylbenzene sulfonate)

• Cationic (e.g. quaternary ammonium chloride)
• Amphoteric (e.g. alkyl substituted imidazoline)
• Nonionic (e.g. ethoxylated long chain alcohol)

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.

Acid Cleaning of Iron and Steel

ACID CLEANING is a process in which a solution of a mineral acid, organic acid, or acid salt,
in combination with a wetting agent and detergent, is used to remove oxide, shop soil, oil,
grease, and other contaminants from metal surfaces, with or without application of heat. The
distinction between acid cleaning and acid pickling is a matter of degree, and some overlapping

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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.

Propelling Abrasive Media

Three basic methods are used to propel the abrasive medium against the surfaces of the
workpieces:

(a) airless abrasive blast blade or vane-type wheels,

(b) pressure blast nozzle systems and
(c) suction (induction blast nozzle systems.

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

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 metal, (b) the nature of the electrolyte, and (c) the surface condition prior to
electropolishing (i.e surface contamination, grain size, and inclusions).

Electropolishing solutions and Operating Conditions

The most widely used electropolishing solutions contain one or more of the concentrated
inorganic acids – sulfuric, phosphoric, and chromic. Sometimes, an inorganic acid, such as
hydrofluoric or hydrochloric acid, or an organic acid, such as acetic, citric, tartaric, or glycolic
acid, can be used with one or more of the concentrated inorganic acids mentioned above.

Equipment and Processing Procedures

Equipment and layout for electropolishing generally resemble those of an electroplating

installation.

Racks. Items to be electropolished are placed with firm electrical contact on a rack to be
positioned on the work bar. The parts are placed so that current distribution will be uniform
when they are immersed between cathodes in the electropolishing solution. Usually, racks are
made of copper or titanium and have spring clips or fingers of bronze, steel, or titanium to
hold the workpieces.

Tanks are made of stainless steel, low-carbon steel, plastic, or fiberglass. Tanks may require
linings of rubber, polyvinyl chloride, polypropylene, or lead, depending on the electrolyte
used. The use of plastic-lined tanks is limited to electropolishing in which the operating
temperature is below that at which the lining can soften.

Cathodes are made of copper, lead, stainless steel, or carbon. The material to be used
depends on the temperature and the kind of electropolishing bath. Cathodes are individual
rods, flat strips, or expanded metal in strips, which can be suspended from the cathode bar in a
pattern for good current distribution.

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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Industrial (Hard) Chromium Plating

HARD CHROMIUM PLATING is produced by electrodeposition from a solution containing

chromic acid (CrO3) and a catalytic anion in proper proportion. The metal so produced is
extremely hard and corrosion resistant.

The process is used for rebuilding mismachined or worn parts, for automotive valve stems,
piston rings, shock rods, the bores of diesel and aircraft cylinders, and for hydraulic shafts.

Hard chromium plating is also known as industrial, functional, or engineering chromium plating.

Principal Uses

Wear Resistance. Extensive performance data indicate the effectiveness of chromium plate in
reducing wear of piston rings due to scuffing and abrasion. The average life of a chromium-
plated ring is approximately five times that of an unplated ring made of the same basis metal.
Piston rings for most engines have a chromium plate thickness of 100 to 200 μm on the wearing
face, although thicknesses up to 250 μm are specified for some heavy-duty engines.

Tooling Application

Various types of tools are plated with chromium for one or more of the following reasons: (a) to
minimize wear, (b) to prevent seizing and galling, (c) to reduce friction, and (d) to prevent or
minimize corrosion. Steel or beryllium copper dies for molding of plastics are usually plated
with chromium.

Worn gages can be salvaged by being built up with hard chromium plate. Also, chromium plate
provides steel gages with good protection against rusting in normal exposure and handling.

Deep drawing tools often are plated with chromium, in thickness up to 100 μm, for improvement
of tool performance or building up of worn areas, or for both reasons.

Decorative Chromium Plating

DECORATIVE CHROMIUM PLATING is differentiated from hard chromium plating by

thickness and by the type of undercoating used. Decorative chromium coatings are very thin,
usually not exceeding an average thickness of 1.25 μm (50 μm). Decorative chromium is
applied over undercoating, such as nickel or copper plus nickel, which impart a bright,
semibright, or satin cosmetic appearance to the chromium. The choice of undercoatings, as well
as the type of chromium applied, can also provide corrosion protection.

Most decorative chromium coatings have been applied using hexavalent chromium processes
that are based on chromic anhydride. However, since 1975, trivalent chromium processes have
become available commercially. They are increasing in importance because of their increased
throwing and covering powers and because they offer environment advantages.

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Hot-Dip Coating of Steels

HOT-DIP COATING processes are used to apply coatings of zinc, zinc-iron, aluminum,
aluminum-silicon alloy, Zn-5A1 alloy, 55A1-Zn alloy, and lead-tin alloy to carbon steels.
Metals such as chromium and titanium cannot be applied to steel by hot dipping because of their
high melting points. Tin, which prior to 1937 was applied only by hot dipping, is now almost
always electrodeposited. This is because it is very difficult to produce the thin and uniform
coatings required for tinplate by means of hot dipping.

The hot-dip process consists of immersing the steel in a molten bath of the coating metal. Zinc
coating (galvanizing) protects steel galvanically because the zinc is anodic to the steel base metal
and therefore corrodes preferentially in most environments. Hot-dip galvanizing affords
adequate atmospheric-corrosion protection to steel. Aluminum hot-dip coatings provide carbon
steels with resistance to both corrosion and heat, in many environments, aluminum protects steel
gavanically in much the same way as zinc.

Zinc-aluminum and aluminum-zinc alloys are also applied to steel by hot dipping. Heating
aluminized steel results in the formation of an iron-aluminum intermetallic compound that resists
oxidation at temperatures up to approximately 800°C. Aluminized steel is often used where heat
resistance is required – for example, in automotive exhaust systems.

Hot-dip lead coatings are sometimes used on steel that will be exposed to sulfuric acid fumes or
other aggressive chemical environments. Terne plate, a lead-tin alloy coating, gives more
protection than pure lead coatings and is solderable.

Hot-Dip Galvanised Coatings

Hot-dip galvanizing is a process in which an adherent, protective coating of zinc and zinc-iron
compounds is developed on the surfaces of iron and steel products by immersing them in a both
of molten zinc. The protective coating usually consists of several layers. Those closest to the
basis metal are composed of iron-zinc compounds; these, in turn, can be covered by an outer
layer consisting almost entirely of zinc.

The complex structure of layers that comprise a galvanized coating varies greatly in chemical
composition and physical and mechanical properties, being affected by chemical activity,
diffusion, and subsequent cooling. Small differences in coating composition, bath temperature
time of immersion, and rate of cooling or subsequent reheating can result in significant changes
in the appearance and properties of the coating.

Iron and Steel Substrates

The chemical compositions of irons and steels, and even the forms in which certain elements
such as carbon and silicon are present, determine the suitability of ferrous metals for hot dip
galvanizing and may markedly influence the appearance and properties of the coating. Steels
that contain less than 0.25% carbon, less than 0.05% phosphorus, less than 1.35% manganese
and less than 0.05% silicon, individually or in combination, are generally suitable for
galvanizing using conventional techniques.

To avoid brittleness of the iron-zinc alloy layer in cast iron materials, substrate iron must be low
in phosphorus and silicon; a preferred composition may contain approximately 0.01%
phosphorus and about 0.12% silicon.

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Cleaning before Galvanizing

Degreasing. Organic contaminants can be remove from the work by several methods. The most
common of these in the post fabrication hot dip galvanizing process is the use of heated alkaline
cleaning baths.

Acid Pickling. Aqueous solutions of sulfuric acid or hydrochloric acid are generally used to
remove mill scale and rust from steel parts before galvanizing. These pickling solutions can
either be sulfuric acid, 3 to 10 wt% or hydrochloric acid, 5 to 15 wt%. To increase effectiveness,
sulfuric acid solutions are always used hot at 60 to 79°C, to avoid excessive fuming. To avoid
overpickling, inhibitors are often used with both sulfuric and hydrochloric acid solutions.

Fluxing is accomplished by immersing the workpiece in an aqueous flux solution or by

maintaining a flux blanket on the surface of the molten zinc bath. A combination of these two
techniques is often used. The fluxing agent is usually a zinc-ammonium chloride salt.

Phosphate Conversion Coatings

PHOSPHATE COATING is the treatment of iron, steel, galvanized steel, or aluminum with a
dilute solution of phosphoric acid and other chemicals in which the surface of the metal, reacting
chemically with the phosphoric acid medium is converted to an integral, mildly protective layer
of insoluble crystalline phosphate.

Phosphate coatings range in thickness from less than 3 to 50 μm. Coating weight (grams per
square meter of coated area), rather than coating thickness, has been adopted as the basis for
expressing the amount of coating deposited.

Phosphate Coatings

Three principal types of phosphate coatings are in general use: (a) zinc, (b) iron and (c)
manganese. A fourth type, lead phosphate, which was more recently introduced, is operated at
ambient temperatures.

Zinc phosphate coatings can be applied by spraying, by immersion, or by a combination of the

two. Coatings can be used for any of the following applications of phosphating: (a) as a base for
pain or oil; (b) as an aid to cold forming, tube drawing, or wiredrawing; (c) for increasing wear
resistance; or (d) for rustproofing.

Iron phosphate coatings were the first to be used commercially. Early iron phosphating
solutions consisted of ferrous phosphate/phosphoric acid used at temperatures near boiling and
produced dark gray coatings with coarse crystals. The term “iron phosphate coating” refers to
coatings resulting from alkali-metal phosphate solutions operated at pH values ranging from 4.0
to 5.0, which produce exceedingly fine crystals.

Although iron phosphate coatings are applied to steel to provide receptive surfaces for bonding
of fabrics, woods, and other materials, they are used chiefly as base coating for subsequent
painting.

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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 425°C 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 900°C, whereas plasma CVD usually operates
at temperature between 300 and 700°C (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.

Typical CVD Materials

Metals. Materials that cannot ordinarily be deposited by electrodeposition – for example, the
refractory metals tungsten, molybdenum, rhenium, niobium, tantalum, zirconium, and hafnium –
are deposited using CVD processes. Typical products produced are crucibles, rocket nozzles,
and other high-temperature components; linings for chemical vessels; and coatings for electronic
components. These refractory metals are deposited at temperatures far below their melting
points or sintering temperatures, and coatings can be produced with a preferred grain size and
grain orientation. For example, tungsten that is deposited by the hydrogen reduction of the
halide and deposition at a lower temperature (500°C) gives a finer grain size with higher strength
(83 MPa) than deposition at a higher temperature (700°C).

Ceramics. The deposition of ceramics involves many different compounds, for example,
titanium carbide (TiC), titanium nitride (TiN), aluminum oxide (Al2O3) and diamond. Coatings
for the cutting tool industry utilize CVD processes, particularly TiC coatings for cemented
tungsten carbide tools and TiN and carbonitride coatings for high-speed tool steels and cemented
carbide tools. Nearly all coating are multilayer systems that combine TiN for lubricity and
galling resistance, A12O3, for chemical inertness and thermal insulation, and TiC and
carbonitride for abrasion resistance.
Diamond Films grown by CVD exhibit outstanding properties approaching natural diamond
such as high electrical resistivity, high optical optical transparency, extreme harness, high
refractive index, and chemical inertness. Different film deposition techniques and system
configurations result in films with different characteristics. Diamond films can be grown using
processing variable of different concentrations of methane in methane-hydrogen gas mixtures
and flow rates. The CVD of diamond requires the presence of atomic hydrogen, which

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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.

Table 1: Typical deposition temperatures for thermal and plasma CVD

Thermal CVD Plasma CVD

Material °C °F °C °F

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

Physical Vapor Deposition

PHYSICAL VAPOR DEPOSITION (PVD) processes involve the formation of a coating on a

substrate by physical deposition of atoms, ions, or molecules of the coating species. There are
three main techniques for applying PVD coatings; thermal evaporation, sputtering, and ion
plating. Thermal evaporation involves heating of the material until it forms a vapor that
condenses on a substrate to form a coating. Sputtering involves the electrical generation of a
plasma between the coating species and the substrate. Ion plating is essentially a combination of
these two processes. A fourth type of process is ion implantation, which does not produce a
coating; instead, high energy ions are made to penetrate into and modify the substrate surface.

Originally PVD was used to deposit single metal elements by transport of a vapor in a vacuum
without involving a chemical reaction. Today, PVD technology has evolved so that a wide array
of inorganic materials (including metals, alloys, compounds, or their mixtures) and organic
compounds can be deposited. The PVD process occurs in a vacuum chamber and involves a
vapor source and the substrate on which deposition occurs. Different techniques arise because of
variations in atmosphere, vapor source heating method, and electrical voltage of the substrate, all
of which contribute to the structure, properties, and deposition rate of the coating. The steps is
deposition occur as follows:

1. Synthesis of the material deposited (transition from a condensed state, solid or liquid, to
the vapor phase, or, for deposition of compounds, reaction between the components of
the compound, some of which may be introduced into the chamber as a gas or vapor).
2. Vapor transport from the source to the substrate.
3. Condensation of the vapors followed by film nucleation and growth.

The PVD process produces coatings for a range of applications including electronics, optics,
decoration, and corrosion and wear prevention. The coatings used for wear applications are
usually hard compounds, and, from the engineer’s point of view, thin-film wear coatings can be

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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 540°C.
Sputtering is often used for depositing compounds; and materials that are difficult to coat by
thermal evaporation techniques. Engineering applications of sputter coatings include:

• Corrosion and oxidation resistance, for example, nickel-chromium, McrA1Y, and

polymers.
• Lubrication, for example, silver, indium, MoS2, PTFE, selenides, silicides, and
tellurides.
• Water resistance, for example, titanium nitride and other nitrides, tungsten,
molybdenum, carbides, borides, and diamond like carbon.

Ion Plating

Process Description. Ion plating is a vacuum coating process in which a portion of the coating
species impinges on the substrate in ionic form. The process is a hybrid of the thermal
evaporation rate being maintained at a higher rate than the atoms that can be sputtered from the

14
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 250°C for steels and 450°C 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

15
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
coatings, ≥10 ions/cm
17 2
commercially in
Electroplated Cr orthopedic devices
Friction Steels Ti plus C implants Dual implants give
≥10 ions/cm
17 2
amorphous surface
layer
Fatigue Ti alloys, steels N, C Implantation effective
≥1017 ions/cm2 for surface initiated
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
catalysis ≥10 ions/cm
17 2
“normal” alloys;
amorphous and
unique surface alloys
possible
Oxidation Superalloys Y, Ce Low effective doses;
≥1015 ions/cm2 implanted species stay
at metal-oxide
interface
Electrical Polymers Ar, F Permits chain
conductivity ≥10 – 10 ions/cm
15 17 2
scissoning, doping;
conductivity
approaches disordered
metal level
Optical: refractive Glasses, electrooptics Li, Ar Chemical doping and
index ≥10 – 10 ions/cm
15 17 2
lattice disorder both
important

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