MITC 2013 　　 2013. 11.

Morioka Mt. Iwate

Boundary Lubrication as Surface Chemistry

１． Surface chemistry
２． Chemical Analyses of BL
３． Tribochemical Reaction
４． Conclusions
Iwate University
Shigeyuki Mori
Tribology and Surface Chemistry Photo by Obara
１． Surface chemistry
２． Chemical Analyses of BL
３． Tribochemical Reaction
４． Conclusions
 Simplification
Ball
Oil molecule
Complicated phenomena

shear

Atmosphere
Disk

Contact conditions Materials

Components

Space station
Lubricating contact
Tribology and Surface Chemistry
1
 Friction of clean metals and influence of adsorbed gases
F. P. Bowden and T. P. Hughes, Proc. Roy. Soc., A172 (1939) 263.

Glass chamber
M

X
Q F O Hg diffusion pump
C I R

metal slider metal wire

There is no simple method of determining the nature or the

amount of any impurity which may remain on a metal surface.

　 Study on boundary lubrication under

2
vacuum
 Chemical Processes of Solid Surfaces
0s 10 s 20 s 30 s 　
2007 Nobel prize 　 Time

100 μm 2D
Pt
CO + 1/2O2 → CO2

Prof. Gerhard Ertl CO Chemical

O2 composition
Fe
N2 + 3H2 　　→　 2NH3
Haber-Bosch method(1913) PEEM

3
１． Surface chemistry
２． Chemical Analyses of BL
３． Tribochemical Reaction
４． Conclusions
 Surface analytical tools Where ? What? When?

Chemistry
TOF-SIMS S
bonding FTIR TEM-EELS
Chemical resolution

Raman

XPS XANES
composition Sulfur compounds S
FeS2
AES
FeSO4
Chemical structure
element EPMA FeSR
RSSR
AFM

mm μm nm Size Mechanical
properties
Spatial resolution
Time 4
 Ion gun

Detector
m/e is estimated by time of
flight of secondary ions
Sample
m = (2eU/L2) t2

Advantages of TOF-SIMS
1.High sensitivity less than monolayer
2.High mass resolution chemical characterization
3.High 2D resolution 1 μm

Principle of Time of Flight Secondary Ion Mass Spectroscopy

TOF-SIMS 5
Chemical analysis of boundary films
formed from PTFE in PEEK

PTFE
Bearing composite
PEEK

Boundary film

Steel ring

6
Contact pressure 2 to 12 MPa PEEK + PTFE
Sliding speed 2 m/s 0.5 to 6 wt%
Lubricant oil 40 ℃
7
 Chemical analysis of tribo-films by TOF-SIMS

Chemical image
wha
Distribution of tribo-film
Mass spectrum t？
2D 　 1μm
Chem. structure
where ？ Thickness less than 1 nm

Mass
spectrum

Chemical images of boundary layer from PTFE

in PEEK-PTFE composite 8
 PTFE = (CF2CF2)n

CF2 = 50

300 1000
Mass number

TOF-SIMS mass spectrum of material surface

9
 Contact pressure

Chemical images of CF+ from PTFE on composite

material after tribo-tests at different contact pressures

10
 Seizure was occurred at 20% of the coverage
of PTFE-tribofilm.
120
％）
被 覆 率 　 （(%)

100
ＰＴ Ｆ ＥCoverage

80

60 Seizure
40
PTFE

20

0
0 5 10 15 20 25 30
Contact pressure (MPa)
面圧　（MPa）

Effect of contact pressure on surface coverage of PTFE

PTFE intensity
PTFE Coverage ＝ constant×
Fe intensity
11
 Chemical images of PTFE and steel components on bearing material

①6MPa ②18MPa ③6→18→6MPa

PTFE
（ CF+)

Steel
（ Fe+)

Removal and recovering of tribofilm

12
 Summary

Removal of tribofilm
Contact Pressure

High contact pressure

Formation of tribofilm Recovery of tribofilm

PEEK + PTFE

steel
Low contact pressure Low contact pressure

Time
Formation model of tribofilm from PTFE-PEEK composite
13
 Observation of tribochemical degradation of
nano-lubricant film on hard disks

Lubricant oil (1 nm)

Hard disk
DLC (3 nm)
Magnetic layer

detected by TOF-SIMS
Head

HOCH2CHCH2OCH2-CF2O(CF2CF2O)m-(CF2O)nCF2-CH2OCHCH2OH
HO OH

Perfluoropolyether (PFPE) oil

14
 Rotating assembly

Tribo-tester installed in TOF-SIMS

15
 50μ ｍ coating ： Al2O3 ， TiN ， DLC ， c-BN
0.5μ ｍ
Si tip

10 mm

slider
Analyzing position
1.8 inch magnetic disk

Fomblin Z-dol

Conditions
load ： 0.2 ～ 0.8 mN
velocity ： 8 rpm
(0.01m/s)
Friction tester of a hard disk in the main chamber of TOF-SIMS
16
 2.5
Intensity ， 106 　 counts

2.0 Mass spectrum of hard disk

1.5 C+
CF+
1.0
C2F5+
0.5 CFO+ CF3+ C2F4+
CF2+
0
0 50 100 150 200
Mass (amu)

Chemical image of friction track

What? and Where? CF+

Friction track
20 µm

Al2O3

Original surface
17
 Chemical image of friction track

?
Intensity ， counts

C+ Component in friction track

40000
27
20000
0
CF+
-20000
CF2+ CF3+ In original surface
-40000 CFO +

C2F4+
C2F5+

0 50 100 150 200

Mass number (amu)

Subtracted mass spectrum of TOF-SIMS

Al2O3 slider ， 0.8mN ， friction repeated 　
100 18
 600
（ a ）　 track Al+ 　
C2H3+ TOF-SIMS
400 sapphire(Al O3)
20 2µm analysis
Al +
Ion intensity, cps

200
Disk
8000
26.6 26.8 27.0 27.2 27.4
600 （ b ）　 original surface
C2H3+ Sapphire(Al2O3)
400

200 Disk

0 Material transfer of Al
26.6 26.8 27.0 27.2 27.4 on disk surface

250
　 Al species 　⇒　
AlF4- wher
200 (c) track
e？
150 （ negative ion)
100 Chemical wear
50 Al2O3 + (CF2O)
0 AlF3 + CO2
102.6 102.8 103.0 103.2 103.4
mass 19
 CF+

(a) 　 CF+ chemical image

(b) Profile of ion intensity

20

CF ＋ intensity ， Counts 15

10
　　　 lubricant loss
5

0
0 20 40 60 80 100 120
Position ， μ ｍ
20
 Fragment ion ：　 C2F4+

Lubricant loss ， Counts×μm

60

40

Lewis acid
20

0
Al2O3 TiN DLC ｃ‐ BN

Slider materials

　　 Effect of slider material on lubricant loss

load ： 0.8 mN, speed ： 8 rpm, friction repeated ：

400
lubricant ： FOMBLIN 　 ZDOL
21
 Long life of head-disk interface(HDI)

Al2O3 ・ TiC
hard DLC
Chemically stable DLC lubricant(1 nm)

Long lige

TOF-SIMS analysis

3D analysis of chemical structure at friction truck

To develop a new tribo-system for HDI

A better combination of lubricant and material
22
 Tracer method using stable isotopes

Organic additives Organic contaminants

C, H, O
Stable isotope as a tracer
2
H(D), 13C, 18O

Analysis with TOF-SIMS

23
 Lubrication of nitrides with ethyl alcohol

CH3CH2OH CD3CD2OH
TiN or CrN?
Friction coefficient

TiN CrN

CrN

Time, s

Wear track Outside

Surface product analyzed by TOF-SIMS
24
１． Surface chemistry
２． Chemical Analyses of BL
３． Tribochemical Reaction
４． Conclusions
 Boundary films are formed through tribochemical reactions.
Ball
Causes of tribochemical reaction
Mechanical Energy

・ ・ ・・ ・・ ・ ・・
・
Disk
Base oil additive

Reaction Conditions Surface Activities

High temp. + high pressure nascent surface
defect
radical site
Space station ・・・・・・
Tribology and Surface Chemistry
25
 Monitor with Q-mass

adsorption desorption

Organic contaminant
Surface defects Metal oxide

Nascent surface

Monitoring the chemical process on nascent surface

26
 Ion gauge
Variable leak valve
Friction force To TM pump

load ball
Lub. oil disk

Q-mass
Magnetic rotating assembly

Fig.6 Experimental apparatus with Q-mass

Table 1 Table 2 Test piece
Conditions
Sliding speed 2, 3, 4, 5, 6 cm/s
Ball Disk
Load 2, 4, 8, 12, 16 N
Material 52100
Temp. R.T.
Diameter 6.25mm 20mm
Vacuum less than 2×10-4 Pa 27
 start stop Au
12

10 adsorption
m/e = 82
8
Intensity, 10-9 A
6

4 m/e = 78

0.6
desorption m/e = 84
0.4
0.2
0 20 40 60 80 100
Time, s

Gold becomes to be active chemically by scratching

+ H2
Au
Catalytic dehydrogenation and hydrogenation of olefin by nascent surface of Au
28
 Additives are effective under
Monitor with Q-mass severe condition Mild condition

Non-polar compd. Polar compd.

RSSR (RO)3P=O EP additives
adsorption desorption

Organic contaminant
Surface defects Metal oxide

Nascent surface

Monitoring the chemical process on nascent surface

29
 Load H2, CH4 ・・・
Hydrocarbon oil

Organic contaminant Active sites on nascent surface

ball

Metal oxide
Steel disk
Catalytic effect

Frictional heat friction

Tribochemical decomposition of hydrocarbon oil

30
Rate of gas formation
Decomposition of hydrocarbon oil
Rd=C2(P2-P)/kT=C2ΔP/kT sliding

Gas evolution during lubrication (MAC, 2cm/s, 8N, 4km)

MAC: multi-alkylated cyclohexane

31
 Conclusions
Boundary lubrication from the viewpoint of surface chemistry

1. Chemical analyses of boundary layers

TOF-SIMS is a powerful tool to analyze boundary films and

tribochemical reactions.

TOF-SIMS analyses revealed that very thin layer of PTFE was

removed at higher contact pressure and was recovered under the
sliding condition of low contact pressure.

It was found that thin layer of PFPE oil was decomposed catalytically
by Al2O3 and TiN as a slider material, but the decomposition was
deactivated by DLC and c-BN coating. Chemically inert coatings such
as DLC make a longer life of HDI.

Stable isotopes such as D(2H), 13C and 18O can be used as a tracer
to detect boundary film without the effect of organic contamination.
2. Nascent surfaces of metals as a active source of tribochemical
reactions are characterized by our method.

Even gold becomes to be active chemically and benzene decompsed

on nascent gold surface.

Sulfide is more active on nascent steel surface than phosphate.

EP additives should be selected depending on lubricating conditions;
Sulfides and phosphates are effective under severe and mild conditions,
respectively.

It was found that hydrocarbon oil was decomposed by the effect of

nascent surface and temperature rise at mechanical contact. Phosphate
is more effective to reduce the decomposition than sulfide.
Thank you for your attention

Photo by Obara