LUBRICATION BY DIAMOND AND DIAMONDLIKE CARBON COATINGS

Kazuhisa Miyoshi

National Aeronautics and Space Administration

Lewis Research Center

Cleveland, Ohio 44135

ABSTRACT

Regardless of environment (ultrahigh vacuum, humid air, dry nitrogen, or water), ion-beam-deposited

diamondlike carbon (DLC) and nitrogen-ion-implanted, chemical-vapor-deposited (CVD) diamond films had low

steady-state coefficients of friction (<0.1) and low wear rates (< ! 0-6 mm3/N-m). These films can be used as effective

wear-resistant, self-lubricating coatings regardless of environment. On the other hand, as-deposited, fine-grain

CVD diamond films; polished, coarse-grain CVD diamond films; and polished and then fluorinated, coarse-grain

CVD diamond films can be used as effective wear-resistant, self-lubricating coatings in humid air, in dry nitrogen,

and in water, but they had a high coefficient of friction and a high wear rate in ultrahigh vacuum. The polished,

coarse-grain CVD diamond film revealed an extremely low wear rate, far less than 10-1° mm3/N.m, in water.

INTRODUCTION

Presently, modem diamonds fall into four distinct categories: natural, high-pressure synthetic, chemical vapor

deposited (CVD), and diamondlike carbon (DLC) (Pierson, 1993). In the last 100 years or so, the scarcity and high

cost of natural diamond have been challenged by the large-scale production of synthetic diamond. Although highpressure synthetic and natural diamonds are used in the industrial market (particularly in wear and abrasive applications), their use in tribological applications is limited by small size and high cost (Gigl, 1989) and the need to be

bonded to a substrate in a separate operation.

CVD diamond and DLC, the so-called new diamond materials, offer a broader potential than natural and highpressure synthetic diamonds because size and eventually cost will be less of a limitation. For example, CVD

diamond has been uniformly deposited on a 20-cm-diameter area, and DLC has been deposited on a 200-cm-long

knife-edge by a reactive-ion-plating technique (Murakawa, 1990). For large-area (>5 mm 2) applications, CVD

diamond and DLC are the only forms of diamond that seem economically viable.
CVDdiamond-filmtechnologylookspromising, although researchers are still tackling problems with enhancing

adhesion to substrates (including steel), speeding up deposition (production) rates, and lowering costs (Feldman

et al., 1995). CVD and DLC diamond films could edge into tribological and tooling applications. In NASA's

perspective, diamond's excellent properties can suit it for coatings on triboiogical components and parts, such as

valves and bearings in the harsh environment found in internal combustion and jet engines and in spacecraft. These

films open the door to tribology technology and design engineering that can take full advantage of diamond's

intrinsic properties in such areas as solid-lubricating, wear-resistant, erosion- and corrosion-resistant, and protective

coatings. These materials offer lively new solutions to important engineering problems and exciting challenges to the

tribologist or designer who seeks to exploit their cost-effective potential. Developing safe and economic applications

for diamond materials that can compete with conventional tribological materials requires understanding their

behavior and taking innovative approaches to manufacturing.

As-deposited CVD diamond film indeed has friction and wear properties similar to those of natural and synthetic

diamonds in a variety of environments (Miyoshi et al., 1992, 1993). The tribological properties of the diamond

materials, like those of conventional lubricating materials (e.g., graphite and molybdenum disulfide), vary with the

environment, possessing a Jekyll-and-Hyde character. For example, diamond is one of the slipperiest materials, and

is similar to polytetrafluoroethylene in terrestrial environments (Tabor, 1979; Bowden and Hanwell, 1966). However,

when a fresh atomically, clean diamond surface contacts an atomically clean counterfacing material, strong bonds

form between the two materials. In this case, diamond possesses high friction, low abrasion resistance, and low wear

resistance (Tabor, 1979; Bowden and Hanwell, 1966; Miyoshi and Buckley, 1980). To some degree, this situation

also applies to sliding contacts, where fresh surfaces are continuously exposed by the counterfacing material.

Because direct contact with fresh surfaces is unavoidable under actual sliding conditions, the tribological performance of clean, unlubricated diamond is of paramount importance.

Getting the best performance from CVD diamond and DLC as solid-film lubricants and/or wear-resistant barriers

for many moving mechanical assemblies requires a good understanding of CVD diamond and DLC themselves, the

counterfacing materials, and the type of environment and operation.
Theinvestigationdescribed herein examined the lubrication, friction, and wear properties of fine-grain CVD

diamond films, surface-modified CVD diamond films, and ion-beam-deposited DLC films in four environments:

humid air, dry nitrogen, ultrahigh vacuum, and water.

MATERIALS

The investigation encompassed four types of relatively smooth surfaces (6 to 37 nm rms) of as-deposited and

surface-modified CVD diamond films: (1) as-deposited, fine-grain diamond; (2) polished, coarse-grain diamond;

(3) polished and then fluorinated, coarse-grain diamond; and (4) polished and then nitrogen-ion-implanted, coarsegrain diamond. In addition, two types of smooth surfaces of ion-beam-deposited DLC films were investigated: (1)

DLC deposited at an ion energy of 1500 eV and (2) DLC deposited at an ion energy of 700 eV.

Wu et al. (1992a, 1993, 1995), Murakawa and Takeuchi (1991), and Miyake (1994) give details of CVD diamond

and DLC deposition and modification techniques. Briefly, the as-deposited, fine-grain diamond films were produced

on the flat surfaces of silicon, silicon nitride, and silicon carbide substrates by microwave-plasma-assisted chemical

vapor deposition (Wu et al., 1992a). The polished, coarse-grain diamond films were produced on the flat surfaces of

silicon nitride substrates by hot-filament chemical vapor deposition using a 1:100 mixture of methane (CH4) and

hydrogen (H2) (Murakawa and Takeuchi, 1991). The fluorinated, coarse-grain diamond films were produced by

exposing polished CVD diamond film to carbon tetrafluoride (CF4) plasma using radiofrequency (13.56 MHz)

power at 1.3 W/cm 2 for 10 min and a flow rate of 10 ml/min at 8 Pa (Miyake, 1994). The nitrogen ion-implanted,

coarse-grain diamond films were produced by impacting nitrogen ions into polished CVD diamond film using an

accelerating energy of 35 keV, resulting in a dose of 5x1016 ions/cm 2 in a calculated mean depth of 47 nm (Wu et

al., 1993). The DLC films were deposited on silicon by the direct impact of an ion beam composed of a 3:17 mixture

of argon (Ar) and CH 4 at a radiofrequency power of 99 W and ion energies of 1500 or 700 eV. DLC film thicknesses

ranged from 520 to 660 nm (Wu et al., 1995).
EXPERIMENT

Avarietyof analytical techniques was used to characterize CVD diamond and DLC films: scanning and transmission electron microscopy (SEM and TEM) to determine surface morphology and grain size and to study wear

surfaces and wear debris; Rutherford backscattering spectroscopy (RBS) and hydrogen forward scattering to identify

impurities (if any) in the films and to determine carbon and impurity concentrations; Raman spectroscopy and

Fourier transform infrared spectroscopy (FTIR) to characterize carbon bonding and structure; x-ray photoelectron

spectroscopy (XPS) to characterize surface chemistry; x-ray diffraction to determine the crystal orientation; and

surface profilometry and scanning probe microscopy to determine film surface morphology, roughness, and wear.

Unidirectional, rotating sliding friction experiments were performed at room temperature in humid air (40%

relative humidity), in dry nitrogen (<1% relative humidity), in ultrahigh vacuum (10 -7 Pa), and in distilled water.

The friction apparatus used in the investigation was mounted in a chamber (Fig. 1). The apparatus can measure

friction in a variety of environments including humid air, dry nitrogen, ultrahigh vacuum, and water. All experiments

were conducted with CVD diamond, surface-modified CVD diamond, and DLC films in contact with CVD diamond

pins (radius, 1.6 mm) at a load of 0.49 N (a mean Hertzian contact pressure of approximately 2 GPa) and at a

constant rotating speed of 120 rpm (sliding velocity, 31 to 107 mm/s depending on the range of wear track radii

involved in the experiments). The friction force was continuously monitored during the friction experiments. Film

wear volumes were obtained by measuring the average cross-sectional area determined from stylus tracings across

the wear tracks at a minimum of eight locations in each track. Then, the average cross-sectional area of the wear

track was multiplied by the wear track length. The wear rate, known as the dimensional wear coefficient, is defined

as the volume of material removed at a unit applied load and in a unit sliding distance expressed as cubic millimeters

per newton-meter.

RESULTS

CVD Diamond and DLC Films

Figure 2 presents typical Raman spectra of as-deposited, fine-grain CVD diamond film; surface-modified CVD

diamond film; and as-deposited DLC film at ion energies of 1500 and 700 eV. In addition, Table I shows a comparison of some of their characteristics.
TheRamanspectrumoftheas-deposited, fine-grainCVDdiamondfilmcontainedthediamondformofsp3-

bondedcarbonat1332cm-1aswellastheG-andD-bandnondiamondformsofcarbon(Fig.2(a)).TheG-band

Ramanshiftsareattributedtothesp2-bonded carbon,whereastheD-bandRamanshiftsareattributedtothedisorderednondiamondcarbonpresentintheCVDdiamondfilm.AlthoughthescatteringefficiencyofspZ-bonded

carbonismorethan50timesthatofsp3-bonded carbon(WadandSolin,1981),theas-deposited, fine-grainCVD

diamondfilmactuallycontainedmuchmoreofthelatter(diamond) formofcarbonthanmaybeinferredfrom

Figs.2(a)to(c).However, thefilmalsocontainedaconsiderableamountofnondiamondcarbon.Thefilmconsisted

ofcarbon,hydrogen, andsomeelementsfromthesubstratematerial,suchassilicon.Thehydrogenconcentration

wasestimatedtobe2.5at.%.Thefilmwasprimarilypolycrystalline, thecrystalliteswereorientedalongthe(110)

directionandhadagranulatedorspheruliticmorphology, andthegrainsizesrangedfrom20to 100nm.The

surfacescontainedsphericalsperitiesrangingfrom6to37nmrms.

IncomparisonwiththeRamanspectrumoftheas-deposited, fine-grainCVDdiamondfilm,theRamanspectrum

ofthepolished, coarse-grainCVDdiamondfilmcontainedmoreofthediamondformofsp3-bonded carbonat

1332cm-1(Fig.2(b)).Thecoarse-graindiamondfilmconsistedprimarilyofcarbon;thehydrogenconcentrationwas

estimatedtobelessthan1at.%.Thefilmwasprimarilypolycrystalline, thecrystalliteswereorientedalongthe

(111)direction,andthegrainsizewasapproximately 10_m.Themeansurfaceroughnesswas25nmrms.

IncomparisonwiththeRamanspectraoftheas-deposited, fine-grainandpolished, coarse-grainCVDdiamond

films,theRamanspectrumof thefluorinated, coarse-grainCVDdiamondfilmcontainedmoreofthediamondform

ofsp3-bonded carbonat1332cm-1(Fig.2(c)).Theintensityofthesharpeakat1332cm-1,characteristic ofthe

diamondformofsp3-bonded carbon,increased(inascendingorder)forfine-graindiamond, polisheddiamond, and

fluorinateddiamond. ThemeansurfaceroughnessofthefluorinatedCVDdiamondfilmwas8nmrms.Thesurface

morphologywasalmostthesameasthatofthepolishedCVD diamond film.

The nitrogen-ion-implanted, coarse-grain CVD diamond film contained primarily amorphous, nondiamond forms

of carbon in its surface layer. The Raman spectrum (Fig. 2(d)) of this diamond film is quite different from those of

the previous three CVD diamond films (Figs. 2(a) to (c)). It shows an extremely small characteristic diamond peak at

1332 cm -1 and a broad characteristic nondiamond carbon peak near 1530 cm -1. Nitrogen ion implantation produced

a thin layer of amorphous, nondiamond carbon in the surface region of the coarse-grain CVD diamond film
(Wuetal.,1993).Thenitrogenionspenetratedtoacalculatedmeandepthof47nm,andthemeansurfaceroughness

was6nmrms.ThesurfacemorphologywasalmostthesameasthatofthepolishedCVDdiamondfilm.

TheDLCfilmscontainedprimarilyamorphous, nondiamondcarbon.Thecharacteristic damondpeakisabsent

fromthemicro-Ramanspectraoftheion-beam-deposited DLCfilms(Figs.2(e)and(f)).ThegraphiticspE-bonded

carbon(G-band)peakissharper andthedisorderednondiamondcarbon(D-band)ismoreprevalent intheRaman

spectrumoftheDLCfilmdepositedat1500eVthaninthatoftheDLCfilmdepositedat700eV.Thehydrogen

concentrationwaslowerintheDLCfilmdepositedat1500eVthaninthatdepositedat700eV.Thecompositions of

theDLCfilmsdepositedat1500and700eVwere,inatomicpercent,C59H36Arl. 8andC57H42Ar0.8 , respectively.

The ratio of carbon to hydrogen for the DLC film deposited at 1500 eV was 1.64; that for the DLC film deposited at

700 eV was 1.36. The mean surface roughnesses of the DLC films deposited at 1500 and 700 eV were 22 and

14 nm rms, respectively.

Coefficients of Friction and Wear Rates

Figure 3 presents the steady-state (equilibrium) coefficients of friction and wear rates at room temperature in

humid air (40% relative humidity), in dry nitrogen (<1% relative humidity), in an ultrahigh vacuum (10 -7 Pa), and in

water for the same films as in Fig. 2. For a direct comparison, the coefficients of friction and the wear rates were

plotted from 0.01 to 1 and from 10-l° to 10-3 mm3/N.m, respectively. An effective wear-resistant, self-lubricating

material must generally have a coefficient of friction less than 0.1 and a wear rate less than l0 -6 mm3/N.m.

The results presented in Fig. 3 indicate that both the steady-state coefficients of friction and wear rates of the

CVD diamond and DLC films depended on the environment. Conditions that reduced friction, such as a particular

combination of environment and material, usually reduced wear rate as well.

The as-deposited, fine-grain CVD diamond film (Fig. 3(a)) had a low coefficient of friction (<0.1) and a low

wear rate (order of 10-6 mm3/N.m) in three environments: humid air, dry nitrogen, and water. However, in ultrahigh

vacuum it had a high coefficient of friction (>0.1) and a high wear rate (order of 10--4mm3/N.m), which are not

acceptable for solid-film lubrication applications. In an ultrahigh vacuum, removing some contaminant surface film

from the contact area resulted in stronger interfacial adhesion between the diamond pin and the diamond films and
raisedthecoefficient of friction, and accordingly, the wear rate. These results are consistent with previous results

(Miyoshi et al., 1993). The increase in friction and wear was attributed to removing the adsorbed contaminants from

the surface by sliding in an ultrahigh vacuum at room temperature.

Like the as-deposited, fine-grain CVD diamond film, the polished, coarse-grain CVD diamond film (Fig. 3(b))

had low friction and wear in humid air, dry nitrogen, and water and high friction and wear in ultrahigh vacuum.

Interestingly, the polished, coarse-grain CVD diamond film revealed an extremely low wear rate, far less than

10-10 mm3/N.m, in water.

The fluorinated, coarse-grain CVD diamond film (Fig. 3(c)) also had friction and wear properties similar to those

of the as-deposited, fine-grain diamond film and the polished, coarse-grain diamond film: low in humid air, dry

nitrogen, and water and high in ultrahigh vacuum.

The nitrogen ion-implanted CVD diamond film (Fig. 3(d)) had low friction and wear, regardless of environment.

This result is consistent with the friction and wear properties of carbon-ion-implanted CVD diamond film (Wu et al.,

1993; Miyoshi, 1995a). The effect of ion implantation on friction and wear is discussed later under Mechanism of

Lubrication. Similar to the nitrogen-ion-implanted diamond film, the DLC films deposited at both 1500- and 700-eV

ion energy (Figs. 3(e) and (10) had a low coefficient of friction (<0.1) and a low wear rate (<10 -6 mm3/N.m) regardless of environment.

Wear Behavior

SEM observations (Fig. 4) indicate that wear debris particles (submicrometer to micrometer in size) were generated by sliding action on the surfaces of the diamond films, the DLC films, and the diamond pins. Much finer

particles were generated on the surfaces of the nitrogen-ion-implanted diamond films and the ion-beam-deposited

DLC films than on the surfaces of the as-deposited, fine-grain diamond; polished, coarse-grain diamond; and

fluorinated, coarse-grain diamond films. These finer particles primarily resulted from the wear and removal of

amorphous, nondiamond carbon by sliding.
DISCUSSION

MechanismofLubrication

TheBowden-Tabor model of metallic friction provides a starting point for understanding how CVD diamond

and DLC films can reduce friction (Bowden and Tabor, 1964; Singer, 1992). If the plowing contribution in friction is

neglected, the friction arising between the films and a CVD diamond pin is described by the equation _t = sAIW

(Bowden and Tabor, 1964) or p o_ ),A (Miyoshi, 1995b) because the surfaces of fine-grain CVD diamond, surfacemodified CVD diamond, and ion-beam-deposited DLC films are smooth. In these equations, la is the coefficient of

friction, s is the shear strength of the contact area (junction), A is the true contact area, W is the normal contact load,

and ? is the surface energy.

Figure 5 illustrates how the friction and the surface condition can vary with the material and the environment.

With adsorbed contaminants (water vapor, carbon oxides, and hydrocarbons usually about 2 nm thick), the hard

diamond film provided a small contact area A, minimized penetration of the diamond pin (accordingly, plowing will

be negligible), and either reduced the shear strength s or maintained the low surface energy _/of the contact area

(Fig. 5(a)). When the model of dangling carbon bonds of diamond (Gardos, 1994; Holmberg, 1993) was applied to

Fig. 5(a), these bonds could be terminated with surface contaminants (hydrogen, hydroxyl groups, and organic

radicals on CVD diamond films and high-pressure synthetic diamonds), providing a low friction in terrestrial (or

nonvacuum) environments. For these reasons, the coefficients of friction for the as-deposited, fine-grain diamond

films; the polished, coarse-grain diamond films; and the fluorinated, coarse-grain diamond films studied in this

investigation were low in humid air and in dry nitrogen.

Removing some of the contaminant surface layers from the contact area (Fig. 5(b)) resulted in stronger interracial

adhesion between the diamond pin and the diamond film and accordingly raised the coefficient of friction. Contaminant surface layers were removed by repeatedly sliding the pin over the same track in ultrahigh vacuum. The hard

diamond film provided a small contact area A and minimized penetration of the diamond pin (accordingly, plowing

will be negligible). Removing adsorbates (contaminant layers) from the contact area enhanced adhesion and

increased either the shear strength s or the surface energy 3' of the contact area. When the model of dangling carbon

bonds (Gardos, 1994; Holmberg, 1993) was applied to Fig. 5(b), these bonds formed a strong carbon-carbon bonds,
providinghighfrictioninaspaceorvacuumenvironment. Forthesereasons, thesteady-state coefficientsoffriction

fortheas-deposited, fine-graindiamondfilms;thepolished, coarse-graindiamondfilms;andthefluorinated, coarsegraindiamondfilmswereextremelyhighinultrahighvacuum.

Figures5(c)and(d)represent thecaseofthenitrogen-ion-implanted, coarse-grainCVDdiamondfilminsliding

contactwithadiamondpin.Theionimplantationprocesses producedathinsurficiallayer(<0.1_tmthick)of

amorphous, nondiamondcarbononthediamondfilm.Thissurfacelayerhadlowshearstrengths or low surface

energy ), at the contact area. Further, because the nondiamond carbon surface layer was thin enough (<0.1 p.m), the

true contact area resulting from the high elastic modulus and hardness of the underlying diamond, which largely

supported the applied load, was small. In general, the combination of either low shear strength or low surface energy

of the thin, nondiamond carbon surface layer and the small contact area gave low coefficients of friction (<0.1) for

the nitrogen-ion-implanted CVD diamond regardless of environment. Thus, disordering the diamond surface with

ion implantation created self-lubricating surface conditions on diamond regardless of the environment.

Because the contaminant layer, coupled with a nondiamond carbon surface layer, provided low shear strength s or

low surface energy 7 at the contact area, the nitrogen-ion-implanted, coarse-grain diamond film had a low coefficient

of friction (~0.1) and a low wear rate (10 -7 mm3/N-m) in humid air and in dry nitrogen (Fig. 5(c)). However,

nitrogen ion implantation had little effect on the coefficients of friction in humid air and dry nitrogen, since thin

contaminant layers (such as adsorbed gases, water vapor, and hydrocarbons) are present on every surface of any

solid once exposed to air. On the other hand, in ultrahigh vacuum (Fig. 5(d)), nitrogen ion implantation greatly

reduced the coefficient of friction and greatly increased the wear resistance. In ultrahigh vacuum, the presence of the

nondiamond carbon layer on the fine-grain diamond films reduced the coefficient of friction to _<0.1 and the wear

rate to 10--6mma/N.m, which are acceptable for tribological applications. Thus, the nitrogen-ion-implanted, finegrain diamond film is an effective self-lubricating, wear-resistant coating, not only in air and in dry nitrogen but in

ultrahigh vacuum as well.

Figures 5(e) and (f) represent the case of the ion-beam-deposited DLC film in sliding contact with a CVD

diamond pin. The hydrogenated surface of the DLC film had low shear strength s or low surface energy 7 (with or

without adsorbed contaminants) at the contact area. Further, the true contact area resulting from the relatively high

Vickers hardness (-1500) of the hydrogenated carbon surface, which largely supported the applied load, was small.
Therefore, the coefficients of friction for the ion-beam-deposited DLC film were low (<0.1) regardless of environment. The most important element to be considered in the cases shown in Figs. 5(e) and (f) is hydrogen. When DLC

films contain no hydrogen or only a small amount of hydrogen, they provide a graphite-like friction behavior (i.e., a

low coefficient of friction in a humid environment and a high coefficient of friction in dry, vacuum, or space environments (Miyoshi et al., 1989, 1991; Wu et al., 1992b; Eldemir et al., 1993; Zaidi et al., 1994; Voevodin et al., 1996;

Liu et al., 1996).

A disadvantage of ion implantation technology is that the penetration depth of implanted species is shallow

(0.01 to 0.5 _tm) relative to that of conventional coatings. This shallow penetration may limit the wear life expectancy of the ion-implanted layer and hence limit tribological applications to light-load or short-term operations. On

the other hand, ion-beam deposition makes it possible to produce uniform DLC films that are a few micrometers

thick on large areas and curved surfaces. This greater range of DLC coating thickness, coupled with low friction and

wear, regardless of environment, can lead to a longer endurance (wear) life expectancy and better wear resistance

than those of carbon-ion-implanted CVD diamond films. For example, the endurance life of DLC films with a

coating thickness of 0.5 lxm on CVD diamond is approximately 20 times greater than that of carbon-ion-implanted,

fine-gain CVD diamond with an amorphous, nondiamond 0.05-lam-thick carbon layer (Miyoshi, 1995a). Thus, the

DLC film is also an effective wear-resistant, self-lubricating carbon film regardless of environment.

Mechanism of Wear

The mechanism of wear for the CVD diamond and DLC films studied in this investigation was an adhesive

interaction that caused small fragments (submicrometer to micrometer size) to be removed from the surfaces of both

the CVD diamond pin and the CVD diamond or DLC film (e.g., Fig. 4). Much finer wear particles were generated

on the surfaces of the DLC film and the nitrogen-ion-implanted CVD diamond film than on the surfaces of the

as-deposited CVD diamond, polished CVD diamond, or fluorinated CVD diamond films. The size of the wear

particles generally correlated with the film wear rate: the larger the wear particle, the higher the wear rate.

10
CONCLUSIONS

Fromtheresultsofcharacterization andslidingfrictionexperiments onas-deposited, fine-grain, chemical-vapordeposited(CVD)diamondfilms;polished, coarse-grainCVDdiamondfilms;fluorinated, coarse-grainCVD

diamondfilms;nitrogen-ion-implanted, coarse-grain CVD diamond films; and ion-beam-deposited amorphous

diamondlike carbon (DLC) films in four environments (humid air, dry nitrogen, ultrahigh vacuum, and water), the

following conclusions were drawn:

1. The ion-beam-deposited DLC and the nitrogen-ion-implanted CVD diamond films can be used as effective

wear-resistant, self-lubricating coatings regardless of environment.

2. As-deposited, fine-grain CVD diamond; polished, coarse-grain CVD diamond; and fluorinated, coarse-grain

CVD diamond films can be used as effective wear-resistant, self-lubricating coatings in humid air, dry

nitrogen, and water, although they have a high coefficient of friction and a high wear rate in ultrahigh vacuum.

3. The polished, coarse-grain CVD diamond film has an extremely low wear rate of less than l0 -l° mm3/N-m in

water.

ACKNOWLEDGMENTS

The author would like to thank Drs. R.L.C. Wu, W.C. Lanter, A. Garscadden, EN. Barnes, and

Susan L. Heidger of Wright Laboratory, Wright-Patterson Air Force Base, Ohio, for producing the as-deposited

diamond and DLC films and for the Raman analysis; and Drs. M. Murakawa, S. Miyake, S. Watanabe, and

S. Takeuchi of Nippon Institute of Technology for producing the surface-modified diamond films.

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Vol. 72, No. 1, pp. 110-116.

Wu, R.L.C., et al., 1992b, "Physical and Tribologicai Properties of Rapid Thermal Annealed Diamond-like Carbon

Films, Surface and Coating Technology, Vol. 54/55, pp. 576-580.

Zaidi, H., Le Huu, T., and Paulmier, D., 1994, "Influence of Hydrogen Contained in Hard Carbon Coatings on Their

Tribological Behavior," Diamond and Related Materials, Vol. 3, pp. 787-790.

13
TABLE I._OMPARISON OF CHARACTERISTICS OF DIAMOND AND DLC FILMS

Surface type rrns surface Grain size, Microstructure Dominated

roughness, nm crystal

nm orientation

As-deposited, fine-grain 6 to 37 20 to 100 Polycrystalline (110)

diamond

Polished, coarse-grain 25 10 000 Polycrystalline (111)

diamond

Fluorinated, coarse-grain 8 10 000 Polycrystalline (111)

diamond

Nitrogen-ion-implanted, 6 10 000 Layered structure--amorphous (111)

coarse-grain diamond carbon layer on crystalline diamond

DLC deposited at 1500 eV 22 .... Amorphous ....

DLC deposited at 700 eV 14 .... Amorphous ....

14
Vacuum chamber -_

Turbomolecular

vacuum pump _,

\

\

Speed

pickup -J

/

/

/

/

Speed control --/

Data acquisition

system ---_

/- Vacuum gage

I

\

X

\

\

\

N

s \

/ \

I

I

I

I \

/ \

\

7,. _"

\

\

\

N

\

N

_-- Quadrupole

gas analyzer

"_'_-- Rotary feedthrough

\

\

\

_- Drive motor

\\\'_-- Pneumatic isolation table

Figure 1 ._Chamber tribometer.

15
¢

i

c

¢0

IG)

"E

16x103

(a)

12--

8--

4

0

1000

8x104

(c)

6--

4--

2

0

1332 crrr-1 /_'%_

/

,t '_

%

1200 1400 1600 1800

Raman shift, crn-1

,,'\J \

-'P-J I I I _'I

000 1200 1400 1600 1800

Raman shift, cm -1

10X104

(b)

8--

6--

¢-

-_ 4

2

0

J

1000 1200 1400

'/,

\

\

L ...._

1600 1800

Raman shift, cm-1

12x104

(d)

J \

8-- / !

= / e" 6 --

J

2 _

o _'J I I I "'-_

1000 1200 1400 1600 1800

Raman shift, cm -1

2.0x103

1.6

0.4

0

1000

4xl 03

_)

(e) 3--

-- _/S"" "'Jj ! -- 2

1200 1400 1600 1800

Raman shift, cm-1

..._rJ i

/-

y \

o _J-" I I I

1000 1200 1400 1600 1800

Raman shift, cm-1

Figure 2._Raman spectra. (a) As-deposited, fine-grain diamond film. (b) Polished,

coarse-grain diamond film. (c) Fluorinated, coarse-grain diamond film. (d) Nitrogen-ionimplanted, coarse-grain diamond film. (e) Diamondlike carbon film at ion energy of

1500 eV. (f) Diamondlike carbon film at ion energy of 700 eV.

16
10-3

10-4 E

E

E 10-6

10-7 --

lO-_

(a)

10-10

0.01

O

E

_ <> A r-I E

[]Air

OA NiVogen Vacuum

O Water

I I

0.1 1

Coefficient of friction

lO-3--

10-4--

10-5--

10-6--

10-7 --

10-8 --

10-0 --

(b)

10-1o

0.01

O

A []

[] Air

A Nitrogen

O Vacuum

O Water

o I

0.1

Coefficient of fdclJon

10-3

10-4 E

10-5

E

E 10-6

10-7 --

lO-8-

10-o

Ic)

10-10

0.01

O

[]

O

[] Air

A NN_ogen

0 Vacuum

O Water

I I

0.1 1

Coefficient of fiction

lO-3-

10-4 --

E

10-6--

E

E 10-6--

10-7 --

_ lO-8-

lO-9

la)

10-10

0.01

A

O

© []

[] Air

A Nitrogen

O Vacuum

O Water

I

0.1

Coefficient of _ction

10-3

10-4

E

E 10-6

10-7 --

10-8--

10-o

(e)

10-10

0.01

10-3

-- E 10-4

0 _ 10-5

[] E I0"-6

A O [] Air _ 10-7

A Nibogen _ 10-8

O Vacuum

O Water 10-9

I

0.1

Coefficient of friction

0

_- A i.-I

I

I 10-10

1 0.01 1

[] Air

N_ogen

O Vacuum

O Water

I

0.1

Coefficient of fiction

Figure 3._Coefficients of friction and wear rates of various films in sliding contact with CVD

diamond pins in humid air, dry nitrogen, ultrahigh vacuum, and water. (a) As-deposited, finegrain diamond film. (b) Polished, coarse-grain diamond film. (c) Fluorinated, coarse-grain

diamond film. (d) Nitrogen-ion-implanted, coarse-grain diamond film. (e) Diamondlike carbon

film at ion energy of 1500 eV. (f} Diamondlike carbon film at ion energy of 700 eV.

17
Figure 4.---Scanning electron micrographs of wear debris particles produced

on (a) as-deposited, fine-grain CVD diamond film and (b) Ion-beam-deposited

DLC film after sliding against diamond pins in ultrahigh vacuum.

18
A

F

s

W

3'

Both s and A

or both 3" and A

are small

(a)

Real area of contact

Friction force

Shear strength of junctions

Load

Surface energy (bonding energy)

Humid air or

dry nitrogen

W

I

Both s and A

or both 3" and A

are small

(c)

Nondiamond carbon

Diamond

Adsorbed -

contaminant

Ultrahigh vacuum

Diamond "_

" / / / '" / / /_ "/ "//I/

Substrate/,,"//), ,/|

/_ / /:/:/V/A

(b)

W F

contaminant

(d)

A is small

but s or

3' is large

Both s and

A or both 3"and

A are small

Both s and A

or both 3' and A

are small

(e)

I DLC (hydrogenated carbon)

Adsorbed _

contaminant

(t)

Both s and

A or both 3" and

A are small

Figure 5._ontact between pin and film in humid air, dry nitrogen, and ultrahigh vacuum. (a) and (b) Asdeposited, fine-grain diamond film; polished, coarse-grain diamond film; and fluorinated, coarse-grain

diamond film. (c) and (d) Nitrogen ion-implanted, coarse-grain diamond film. (e) and (f) Diamondlike carbon

film.

19
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1. AGENCY USE ONLY (Leave blank) 2. REPORT DATE

June 1997

4. TITLE AND SUBTITLE

Lubrication by Diamond and Diamondlike Carbon Coatings

6. AUTHOR(S)

Kazuhisa Miyoshi

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)

National Aeronautics and Space Administration

Lewis Research Center

Cleveland, Ohio 44135-3191

9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES)

National Aeronautics and Space Administration

Washington, DC 20546-0001

3. REPORT TYPE AND DATES COVERED

Technical Memorandum

5. FUNDING NUMBERS

WU-505-63-5A

8. PERFORMING ORGANIZATION

REPORT NUMBER

E-10462

10. SPONSORING/MONITORING

AGENCY REPORT NUMBER

NASA TM- 107472

11. SUPPLEMENTARY NOTES

Prepared for the Tribology Conference sponsored by the American Society of Mechanical Engineers, London, United

Kingdom, September 8-12, 1997. Responsible person, Kazuhisa Miyoshi, organization code 5140, (216) 433-6078.

12a. DISTRIBUTION/AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE

Unclassified - Unlimited

Subject Category 27

This publication is available from the NASA Center for AeroSpace Information, (301) 621-0390,

13. ABSTRACT (Maximum 200 words)

Regardless of environment (ultrahigh vacuum, humid air, dry nitrogen, or water), ion-beam-deposited diamondlike carbon

(DLC) and nitrogen-ion-implanted, chemical-vapor-deposited (CVD) diamond films had low steady-state coefficients of

friction (<0. l) and low wear rates (_<10 -6 mm3/N.m). These films can be used as effective wear-resistant, self-lubricating

coatings regardless of environment. On the other hand, as-deposited, fine-grain CVD diamond films; polished, coarsegrain CVD diamond films; and polished and then fluorinated, coarse-grain CVD diamond films can be used as effective

wear-resistant, self-lubricating coatings in humid air, in dry nitrogen, and in water, but they had a high coefficient of

friction and a high wear rate in ultrahigh vacuum. The polished, coarse-grain CVD diamond film revealed an extremely

low wear rate, far less than 10 -10 mm3/N-m, in water.

14. SUBJECT TERMS

Diamond and DLC coatings; Lubrication; Tribology

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