Kutz M. Handbook of materials selection
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1280 MATERIALS SELECTION FOR WEAR RESISTANCE
and Henderson (1991), Beck et al. (1993), Knotek and Loffler (1992), Knotek
and Loffler (1991), Zahner and Menon (1995), Williamson and Bolton (1983).
The selection of specific wear materials for specific applications is reviewed in
Ashby (1992), Bolvari and Glenn (1995), Bamkin and Piearcey (1990), Charles
et al. (1997), Carnes et al. (2000), Edwards (1994), Edwards (1997), Eyre (1991),
Farrow and Gleave (1983), Fischer (1996), Sundaresan (1988), Syan (1994),
Strafford (1996), Subramanian and Strafford (1993), Subramanian et al. (1996),
Shubrook (1996), Glaeser (1992), Hogmark et al. (2000).
6 SUBSTRATE SELECTION
There are several basic principles involved in substrate selection for wear film
deposition. The material has to be compatible with the chemistry of the wear
film deposition and growth environment. The substrate cannot have a coefficient
of thermal expansion that is far greater or less than that of the wear film. This
criterion can be reduced in importance by the use of very thin films that tend
not to build up large internal stresses.
7 SURFACE MODIFICATIONS
The as-grown surfaces of some hard films are not suited for immediate use. The
as-formed surface of some wear materials can be very rough. The degree of
roughness can prevent the use of these materials as bearings if there is no method
of making the surface smooth. These surfaces may be rough or chemically re-
active and require an additional preparative step such as polishing or a ‘‘run in’’
period prior to their use.
Films need to have less than a 0.4-
m peak-to-valley roughness in general
to be used for bearings. Surfaces with roughness greater than 5
m peak-to-
valley roughness have been found to be unacceptable and, in the absence of a
method of making the surface smooth, would prevent the use of these materials
as bearings. Mechanical polishing is preferably avoided to reduce the per-part
finishing cost as well as retain uniform dimensionality.
Making a wear film smooth to begin with reduces the likelihood of introduc-
ing flaws into the film as well as making the process much less expensive.
Smooth wear films may be made by several different methods. These include
polishing, brazing the rough side down, growing the films very thin, or growing
them very smooth initially. Smooth films can be made if the average crystallite
size is small and if there is no room for the crystal to grow laterally. A thin,
pinhole-free film can be grown if crystallites are densely packed. Making the
film smooth initially reduces the likelihood of introducing flaws into the film as
well as making the process much less expensive.
8 FILM THICKNESS
A thin film will allow the physical properties of the substrate material to be
sampled during use. The scale of thickness is completely dependent on the scale
of the system. A thin film might be 0.5
m thick if the maximum foreign particle
size is 0.25
m in diameter where a thick film would be 5
m thick. Similarly,
a thin film might be 70
m thick if the maximum foreign particle size is 20
m
in diameter where a thick film would be 200
m thick. How thick must a film
be to be thick enough? The size and hardness of foreign particulate matter
9 APPLICATIONS AND EXAMPLES OF WEAR MATERIALS 1281
arriving at the bearing surface will determine the thickness of the wear film.
Thickness removal is comparable to cost because of time and material used
during finishing. Mechanical polishing can also be an agent of flaw introduction.
A brittle hard coating that is only a few microns thick would easily run a
through-crack.
9 APPLICATIONS AND EXAMPLES OF WEAR MATERIALS
Wear materials are generally thought of in terms of metallurgical materials sys-
tems. Overall volume of wear materials would certainly demonstrate the impor-
tance of metals and metallurgy. There are a variety of other materials that have
and are being used in wear applications. While the total volume of these ma-
terials combined is small compared to metals, they do represent a significant
fraction of wear materials. Ceramics are slowly being phased in as wear mate-
rials in expected and unexpected places. Ceramics are now being used in high-
performance ball bearing applications as well as high-end cutlery. The studies
by Dellacorte and Steinetz (1994) and Riley (1996) review some of the uses and
methods of selection of ceramics for wear applications.
Polymers have had a traditional role in wear applications from Teflon bearing
sleeves to the rubber tires strapped to the sides of harbor tugboats. The following
works provide some general guidelines for polymer use and selection in wear
applications: An et al. (1997), Besic (1995), Palmese and Chawalwala (1996),
Leger (1989), Price (1987), Wolpers and Hager (1990), Sysoev et al. (1986),
Sladkov et al. (1998), and Tewari and Bijwe (1991).
Stone and natural glass were some of the original wear materials used by
humans. These materials continue to be used into the twenty-first century in
‘‘cutting edge’’ applications as described by Twitchen et al. (1995) and Erting-
shausen (1985).
Injection, stamping, and figure mold surfaces in materials process facilities
face significant wear problems. This type of machinery will lose its dimensional
tolerance over time as it is used. An intricately carved stamping blank would
ideally never change its dimensions. This would reduce long-term production
costs and reduce the amount of mechanical downtime when workers are idled
while waiting for a stamping press to be retooled. The following studies examine
wear materials for this type of application: Clarke (1985), Elfick et al. (1999),
Haggag (1989), Hu et al. (1999), Murray et al. (1997), Bahadur (1993), Ward
et al. (1996b, 1998), Hampson (1994), Gonzalez et al. (1999), Atkinson and
Bristol (1992), Aksit and Tichy (1998), Stack and Pungiwat (1998), and Haugen
et al. (1995).
The purpose of numerous refernces cited above is to provide a resource to
those interested in wear materials selection. References cited range from wear
materials selection criteria to interesting accounts and analyses of wear materials
application and failure. The following references may also be of interest: Blau
and Gardner (1996), Collins (1981), Colombie et al. (1987), Freimanis et al.
(2000), Fu et al. (2000), Gil Sevillano (1997), Hepp et al. (1997), Hornbogen
and Schafer (1981), Middleton and Coupland (1996), Moore (1981), O’Brien
(1982), Peterson and Ramalingam (1981), Samuels et al. (1981), and Wendl and
Wupper (1990).
1282 MATERIALS SELECTION FOR WEAR RESISTANCE
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1287
CHAPTER 42
DIAMOND FILMS
Andrew W. Phelps
University of Dayton Research Institute
Dayton, Ohio
1 HISTORICAL BACKGROUND 1287
2 PROPERTIES OF CVD DIAMOND 1289
3 DIAMOND FILM DEPOSITION 1291
4 MODIFYING CVD DIAMOND 1295
5 DIAMOND FILM ROUGHNESS 1295
6 DIAMOND FILM THICKNESS 1296
7 DIAMOND FILM ADHESION 1297
BIBLIOGRAPHY 1300
1 HISTORICAL BACKGROUND
The formation of diamond by artificial means has been an on-going effort for
much of the last 150 years. Hannay, Moissan, and Parsons all attempted to make
diamond artificially during the nineteenth century. Their claims have been re-
peatedly examined and usually dismissed. Many of the early attempts at diamond
growth did not and still do not fall within the confines of scientific dogma with
regard to high-pressure and temperature diamond synthesis; however, some of
those early efforts are remarkably similar to those used today to make diamond
at low pressures. A review of these early efforts can be found in the book by
Davies (1984). Figure 1 presents a rough timetable to show the activity involved
in diamond synthesis by chemical vapor deposition (CVD).
One early effort at diamond synthesis by Willard J. Hershey in the 1920s to
the 1940s is usually overlooked. He claimed to have made diamond from excess
carbon dissolved in molten iron. According to Hershey, the diamond formation
took place during the rapid freezing of the molten iron mass. The resulting rapid
shrinkage of the iron was supposed to produce a large compressive force on the
carbon and convert it to diamond (Hershey, 1929, 1937; Hershey and Hamersley,
1940). Empirical observation had shown that natural diamond found in its native
kimberlite was probably made deep in the earth and the carbon that diamond
was made from was under a very high temperature and a large pressure at the
time of formation (Bauer, 1968). It was believed that diamonds could be made
synthetically if the very high pressures deep in the earth could be replicated at
a high temperature in the laboratory. However, attempts to make diamond in
ways that did not incorporate the use of large hydraulic presses to create high
pressures such as Hershey’s were not looked on favorably. P. W. Bridgeman
HandbookofMaterialsSelection.EditedbyMyerKutz
Copyright Ó 2002 John Wiley & Sons, Inc., NewYork.
1288 DIAMOND FILMS
Fig. 1 Time line for the development of CVD diamond.
worked for many years on the production of high pressures in the laboratory as
well as on the high-pressure graphite-to-diamond transformation (Bridgman,
1913, 1947) and could be considered the spiritual father of high-pressure and
temperature synthesis of diamond. General Electric was the first to publicly
announce that artificial production of diamond had taken place in 1952 via the
high-pressure–high-temperature press method (Bundy et al., 1955; Strong, 1989)
although ASEA in Sweden was the first to actually achieve high-pressure dia-
mond synthesis (Liander, 1980).
The first, generally acknowledged, successful low-pressure diamond growth
was announced by Eversole in 1962. His work had begun in the late 1940s, but
he waited for conclusive proof of diamond formation before patenting his tech-
nique (Eversole, 1962a, 1962b). He made diamond by the pyrolysis of methane
at low pressure over a diamond substrate and subsequently removing the non-
diamond carbon to produce a net deposit of diamond. This was a very slow and
laborious process and required the measurement of very small weight changes
in the diamond. The amounts of diamond were so small that very precise mea-
surements of less than one percent of weight change were needed to characterize
the deposition process. This work was performed well before the development
of laser-based Raman spectroscopy, the most common laboratory technique used
to identify diamonds since the late 1980s (Knight and White, 1989). Eversole’s
work was reported shortly after the efforts of General Electric captured news-
paper headlines around the world and was summarily ignored. Eversole’s work
may be taken as the historic beginning of today’s efforts in the low-pressure
CVD diamond synthesis and development.
A Soviet research effort was begun in parallel with Eversole in the 1950s on
the pyrolysis of hydrocarbons over diamond substrates, but this early work was
not reported in the western literature until recently (Spitsyn, 1991). J. C. Angus
of Case Western Reserve University took up work on diamond deposition from
the gas phase in the late 1960s (Angus et al., 1968) and apparently inspired the
active Soviet research group to redouble their efforts on low-pressure diamond
synthesis (Derjaguin et al., 1968, 1973). Low-pressure diamond synthesis was
dealt nearly a death blow when Derjaguin was found to have produced a case
study in pathological science with the announcement of polywater. Angus has
said in public that this had the effect of reducing or removing any support he
had for low-pressure diamond development, and he switched to pursue research
on diamondlike carbon (Angus, 1986). Work on low-pressure diamond formation
by the Soviets did not stop as a result of polywater. They continued to work
through the 1970s on many aspects of low-pressure diamond deposition (Spitsyn,
1991).
2 PROPERTIES OF CVD DIAMOND 1289
The Japanese have also been working in the area of carbon film deposition,
diamond-like carbon, and diamond since the 1960s. Based on their Japanese
patent activity, their early efforts appear to mainly have been in the area of films
for electronic materials (Tither et al., 1989). The Japanese were the source of
three fundamental improvements in low-pressure diamond synthesis. They seem
to have been the first to add large amounts of hydrogen to the deposition envi-
ronment. Earlier low-pressure diamond deposition experiments were performed
in environments containing mainly the hydrocarbon feedstock. After a deposi-
tion, the diamond substrate would be cleaned of the nondiamond carbon that
would deposit with the diamond. The diamond substrates did not have to be
removed and cleaned after each pyrolysis by depositing diamond films in a
hydrogen-rich environment. This dramatically improved the growth rate of the
film process. The Japanese were also the first to explore diamond film deposition
with microwave plasmas, radio frequency plasmas, combustion torches, and hot
filaments. Microwave plasma-enhanced chemical vapor deposition (MPECVD)
is now the standard by which all other deposition techniques are judged. The
third improvement was their introduction of Dr. Rustum Roy to diamond film
synthesis in 1985 when he visited a series of Japanese laboratories to explore
cooperative research.
Dr. Roy’s return to the United States with news of the Japanese making
diamond films prompted a strong American research response to either confirm
or disprove the Japanese work (Roy, 1987). Since that time, over half a dozen
companies had been formed to exploit diamond film technology and a industri-
ally funded university consortium of 40 companies had formed within 2 years
of his return. Activity in the field of diamond film deposition peaked around
1990. Six international conferences took place, several industrial and university
centers had been founded for the purpose of diamond research, and a peer-
reviewed journal devoted to the subject was initiated that year. A monthly news
magazine (Diamond Deposition: Science and Technology) with hundreds of sub-
scribers had been founded by that time to keep researchers up to date on the
fast changes occurring on nearly a daily basis in the field. Today, the frenzied
pace of activity in the field has slowed as research on diamond films moves
from a part-time laboratory curiosity to an applied development field where
useful products are gradually being produced (Fig. 2).
2 PROPERTIES OF CVD DIAMOND
CVD diamond may be used in thin-film form for mechanically hard infrared
transmission coatings, machine tooling, electronic devices and substrates, and
coatings for bearings. Thick diamond films may also be used in machine tooling
but also as free-standing optical and infrared windows, electronic substrates, and
bearings. CVD diamond may be made in powder form that can be used as the
starting material for diamond ceramics and diamond filled composites, mono-
sized abrasives, and as feedstock for high-pressure diamond crystal synthesis
(Spear, 1989).
The physical properties of diamond may vary depending on the deposition
method and technique. The general physical properties of diamond films are
closely related to those established for bulk diamond. Many physical phenomena
depend on the type of bonding and the bond termination that is found in a