Thin Solid Films, 95 (1982) 133-142 PREPARATION AND CHARACTERIZATION

133

MECHANICAL, THERMAL AND TRIBOLOGICAL PROPERTIES OF E L E C T R O - AND C H E M O D E P O S I T E D C O M P O S I T E C O A T I N G S *

ERHARD BROSZEIT Institut fiir WerkstoJ~unde, Teehnische Hochschule Darmstadt, Grafenstrafle 2, 61 Darmstadt (F.R.G.) (Received March 29, 1982; accepted April 5, 1982)

By means of chemical (autocatalytic) and electrolytic codeposition of nickel and silicon carbide particles it is possible to produce coatings with enhanced wear and corrosion resistance on metallic and plastic substrates. In the first part of the paper the basic plating technique in relation to the type, form, grain size and activation of the SiC particles will be described. The mechanical properties of the coatings depend on the amount of incorporated particles in the nickel matrix. By activation of the SiC powder the content of particles in the coating can be increased significantly. Mechanical properties such as hardness, strength and elastic modulus improve with increasing content of particles. It will be further shown that the negative influence of a pure nickel coating on fatigue is reduced with a coating of Ni-SiC. This result can be explained by the behaviour of the internal stresses in the coating as a function of the SiC content. The tribological properties of the coatings were tested by an abrasive wear mechanism under lubricated conditions combined with corrosion. The corrosive wear tests were performed under potentiostatically controlled conditions. The high temperature application of these coatings is limited by the thermal decomposition of the SiC particles in the nickel matrix at about 500 C. The coatings were examined by various techniques such as differential thermal analysis, X-ray diffraction and secondary ion mass spectrometry. The influence of different temperatures on the mechanical and tribological properties of the coatings will be described.

1. INTRODUCTION Electrolytic and electroless deposition of composite coatings are well-known techniques for producing protective coatings on metallic and non-metallic parts ~-5. As the plating process takes place in aqueous solutions the maximum temperature in the bath is below 100 C. This is one of the main advantages. A further advantage is the comparatively high deposition rate. *Paper presented at the International Conferenceon MetallurgicalCoatings and ProcessTechnology, San Diego, CA, U.S.A., April 5-8, 1982. 0040-6090/82/0000-0000/$02.75 ElsevierSequoia/Printedin The Netherlands

134

E. BROSZEIT

The matrix materials mainly applied are nickel in the case of electroplating and N i - P in the case of the chemical deposition. Several carbides and oxides such as SiC, TiC, WC, B4C, AI20 3 and SiO z have been used as the particulate material. Among these SiC is mainly applied. Normally the grain size of the SiC particles is 0-3 p~m. The concentration of the powder in the bath is in the range of 0-200 g I-~. To prevent separation of the suspension the bath is magnetically or mechanically stirred or air is blown into it. The incorporation of the SiC particles in the nickel or N i - P matrix depends on the activation of the SiC powder. Figure 1 shows the amounts of incorporated SiC for non-activated material and surface-activated material.

d,

0 I0 ~5

50

"/5

100

150

200

SiC- contenI in the both [~/I]

Fig. 1. A m o u n t of SIC incorporated in Ni SiC coatings activated; C), surface activated.

vs.

SiC content in the electrolyte: 0, non-

2. MECHANICAL PROPERTIES

The hardness of the coating and the residual stresses depend on the amount of incorporated particles in the nickel matrix. In Fig. 2 the influence of the amount of incorporated SiC and AI20 3 on the hardness and the residual stresses for a dispersion coating plated in a Watts-type electrolyte is shown. For both dispersoids the hardness increases with increasing particle content; however, the increase in hardness is more marked for SiC. The internal stresses in the coatings decrease with increasing particle content. The mean grain size of the matrix material was measured with X-ray techniques and also showed a tendency to decrease (from 1200 to 600/~) with increasing particle content. With several agents, e.g. saccharin, it is possible to produce electroplated coatings with increased hardness and compressive stresses. Figure 3 shows the influence of the saccharin content in the electrolyte (Watts type, containing 200 g A120 31- 1) on the hardness and the internal stresses. The hardness increases with increasing additive content, whereas the residual stresses change from tension at low saccharin concentration to compression at concentrations above 0.06 g 1 1 The incorporation of hard particles in the nickel matrix also influences the stress-strain behaviour of the material. Figure 4 shows the reduction in the strain. In

ELECTRO-

AND

CHEMODEPOSITED

COMPOSITE

COATINGS

135

5O0

#00

300
I

\'~ "----L4 3

ZOO

100

0
(a)

Z
BASE

dt

10

~%
(b)

tO

DISPERSOID

CONTENT

%
vs.

MATERIAL, UNCOATED

Fig. 2. (a) H a r d n e s s vs. c o n t e n t o f i n c o r p o r a t e d content.

S i C a n d A 1 2 0 3 ; (b) t e n s i l e s t r e s s e s in t h e c o a t i n g

SiC

500

4OO
300

j J

e:ff 31111, .
zoo
100

WATTS-nickel (200g/[ AtzO 3)

variable saccharine-content

200

E
0

i~100

saccharine-content
0 gll

I00 I
-- - ~ , , - ~ , , , - - , - , ~ , 50

",-,,.v-,-.:

: z

\
-- - -- - - ~ " ~ ' - " ' ~ - ~
/

O.08g/t . . . . ~-- -50 - - - [1.1 g/I . . . . . . . . .

_,oo
-100

20

40

60

80

I00

coating thickness [pm]

F i g . 3. H a r d n e s s a n d i n t e r n a l s t r e s s e s as f u n c t i o n s o f t h e a d d i t i v e c o n t e n t .

o.oz 0.04 o.o6 o.~ {~ socchorine-content [gill

Fig. 5 the change in the Young's modulus as a function of the amount of incorporated SiC is shown. Figures 6 and 7 demonstrate the influence of SiC on the yield limit and the strength. Figure 8 shows the crack surfaces of a pure nickel specimen (Figs. 8(a)-8(c)) and of an Ni-7~oSiC specimen (Figs. 8(d)-8(f)). The ductility of the pure nickel and the brittleness of the composite coatings are clearly demonstrated. The microstructure of the fracture surface (Fig. 8(f)) shows the dispersoids and the plastic deformation of the nickel matrix material. The mechanical properties of the composite Ni-SiC material depend on the amount of dispersoid in the metallic matrix. The hardness, Young's modulus, yield limit and strength increase with increasing SiC concen-

136

E.

BROSZEIT

~,00 200 o

Ni

Ni-SiC
(co. 2% SiC) o 8o0

~OL}
200 0 8gC

Ni-SiC
(co 4%SIC)

Ni-SiC 2~
o ~ strain (CQ 7=/=SiC) 4 5

c[%]

Fig. 4. Stress-strain behaviour of various coatings.

210000
o Q
E

Oo ~

.~o C ....z--~ %

o/,,81
x,
>-

i
......

=o
4oo q w,~ - )o ,::,: Ni-SiC oWb./

1" I
---s

--~--i-o~?.pos!,~-~

Yo:,l,I ~-o

o ooo
~ 600

~l

1
400 C/lh

~L.
.g-

~6o0o0

--i
J [ I

- I

~ O0C/lh,
I I I

0 20~(11 E
z

19~[11

6ooc/lh !
,.s~ ;..- .--~

i /

17O000

.g.

160000
o
[ 1 I 2

l 3

[ 5

I 6
[wt %i

i 7

l 8

o
0 1 2 3 4

o,z'/,t
5

~lLo,
6 7 8

SiC f n c o r p o r o b o n

SiC CONTENT
Fig. 5. D y n a m i c Y o u n g ' s m o d u l u s
vs.

SiC c o n t e n t .

Fig. 6. Yield limit

vs.

SiC c o n t e n t .

ELECTRO- AND CHEMODEPOSITED COMPOSITE COATINGS

137

BOO 700 600

500,
z 400, 300

IEI E-I
o

,~ zoo 100 0 800 70O 600 ~= 500 ~ 400', ~ ' ~ 380'

e

Ni-SiC owb. t~t',

J J I B

zoo
100

400"C/lh- - , - ~

8oo 7O0 600 500 400, 3~,

zoo I00

W -

600%/lh

0 0
1 2

'
3

?Y
4

i]

fL/to
7

SiC
Fig. 7. Strength
vs.

CONTENT

SiC content.

(a)

(b)

(c)

(d)

(e)

(f)

Fig. 8. Crack surfaces of (a)-(c) a pure nickel and (d)-(f) a composite coating.

tration, while the ductility decreases. As the residual stresses also decrease, the fatigue life under rotating-bending conditions in air is raised in comparison with that of the specimens coated with pure nickel (Fig. 9).

138

E. BROSZEIT

#6 qq

1100 1000
--

:",,I

#Z

....

S.
I

900 800
700

m
) +o-

/./
.//+

i
- -

%[- . . . . Ni-P-SiC

"o .~ BOO 5OO

~ a2 --

[co

5%1

~N!-P-

400
onneoling

hme

ZO

300
5

Z60

?o
%
or A1203

I
[C ]

too 2oo 3oo 4oo soo 000 ?oo 0o0 0oo 1ooo lemperolure

SiC-CONTENT

Fig. 9. Fatigue strength vs. SiC

content: 0, SiC; O,

A1203; - -

-, uncoated specimen.

Fig+ 10. Hardness vs. annealing temperature.

x At2 03-J~qP qPJF specim+n

Ni-SiC

m~eci~

Ni-P-SiC

4.~

+I--l+

- -

Ni
c
-~
I

(a)

,~

(a)

~E

*l
~ E
800%

36o, % +2o % +5o,~ 88o,.c ~ lOO 200 300 400 500 600 700 800 900 I000

. . . .

580"C ,.

340 0 100 200 ~,00~00 500 600 700 BOO gO0 1000

(b)

temperolure ~ [C ]

(b)

temperoture [% ] ~

Fig. l 1. Differential thermal analysis results for nickel and Ni-SiC coatings (inert material, ~-A1203;
dO~dr = 20 ~'C rain- 1); (b) difference curve (Ni-SiC values minus nickel values).

Fig. 12. Differential thermal analysis results for Ni-P and N i - P SiC coatings (conditions as in Fig. 11); (b) difference curve (Ni-P-SiC values minus N i - P values).

ELECTRO- AND CHEMODEPOSITED COMPOSITE COATINGS

139

3.

INFLUENCE OF HEAT TREATMENT

The properties of the chemically deposited Ni-P coatings can be improved by heat treatment. Figure 10 shows the variation in the hardness of Ni-P and Ni-P-SiC films with the annealing temperature (annealing time, 2 h) in the range from room temperature to 800 C. The hardness has a maximum at 350 C and decreases at higher temperatures. Except for the hardness values at 800C the hardness curves are similar for both coatings. Electroplated nickel and Ni-SiC coatings show decreasing hardness with increasing annealing temperature. Using differential thermal analysis we demonstrated that at several critical temperatures crystallographic changes and chemical reactions take place (Fig. 11). Strong exothermal peaks are observed at 650 and 880 C. For the Ni-P and Ni-P-SiC coatings differential thermal analysis again shows several critical temperatures (Fig. 12): at 340C (formation of Ni3P ) for both coatings, at 580 C (Ni-SiC reaction) for the Ni-P-SiC coating and at 880 C (partial melting of the eutectic Ni-10~/oP alloy) for both coatings.

~ ' , ~ <, 'Egrg

r~

.;"~

'.,*)21
(a) (b) (c) (d)

Fig. 13. Structure of Ni-SiC coatings annealed at 650 C for (a) 10 s, (b) 5 rnin, (c) 30 min and (d) 2 h.

Figure 13 shows cross sections of an Ni-7~oSiC coating after various heat treatment times at 650C. After 10s no change in the structure is observed. However, after 5min the SiC particles have decomposed and a dark phase (presumably Ni3Si ) has formed in the bright nickel phase. After 30 min a third phase (presumably carbon) has formed at the grain boundaries and in the interior of the dark phase. A 2 h heat treatment changes the structure of the coating again: in a uniform grey matrix (Ni-Si) only black lines (carbon) remain. 4.
TRIBOLOGICAL PROPERTIES

The tribological properties of the electroplated and chemically plated nickel and nickel dispersion coatings were tested in the abrasive wear regime for mild and

140

E. BROSZEIT

i
Ni i Ni-TiC
1o - (co

21oTiC) -

anneetin time 2h 9
-50 E I I I

40

/
--anneeling time 2h--@~/

z4h__/

-lh

"I'
15 7% SiC)

tO0

200

300

z,~

500

600
]

700

800

I000 gO0

lemperoture [ C

Fig. 14. Abrasive wear of nickel, Ni SiC and Ni TiC coatings

vs.

the annealing temperature.

severe abrasive conditions. For the tests a Taber abraser was used. Figure 14 shows the weight loss per revolution in micrograms for Ni-SiC and N i - T i C after heat treatment at temperatures up to 1000 C (annealing time, 2 h). For the pure nickel coating the wear (mild abrasive conditions) decreases slightly with increasing temperature. The Ni-SiC composite coating shows little wear for temperatures up to 350 C in comparison with the nickel coating at the same temperatures. For heat treatment temperatures above 350C the weight loss rises to a m a x i m u m at 650C; above 650 C the wear decreases again. The TiC-containing coatings (2'~o TiC) show the best results over the full range of temperatures. This is due to the better thermal stability of the TiC particles in the nickel matrix. In Fig. 15 the wear behaviour of the chemically deposited N i - P and N i - P - S i C coatings is shown for annealing temperatures up to 800 C. The weight loss for the N i - P coating is relatively high for low annealing temperatures (200C). Heat treatment above 300 C improves the wear properties. A wear minimum was found at 650"C. The dispersion coating N i - P - S i C shows little wear at annealing temperatures up to 350 C. Thermal treatment at high temperatures (400-800 C) leads to a deterioration in the wear properties under mild abrasive conditions. In Fig. 16 the wear properties of a nickel diamond composite coating are compared with the wear behaviour of a boride layer (Fe2B). Under mild and severe conditions the weight losses of the brittle boride layer are respectively 2 and 30 times that of the ductile nickel-diamond composite coating.

ELECTRO- AND CHEMODEPOSITED COMPOSITE COATINGS

141

] Ni-P

"T\
_

b-...
I I

/
o

10

cslox::~ I,~ ~"~:

onneohnglime2h
I I
I I I

o
2O

'1 ~ /
( 5 7*,
0

Ni- P -

SiC

r-I
[C ]
vs.

SiC)

~0 ~in1inn 2h, ? time 0 ~00 200 300 400 500 600 70o ~00 goo ~000
temperature the annealing temperature.

Fig. 15. Abrasive wear of Ni P and N i - P SiC coatings

250

severe obroslon
200 :

25
TABER-~SER

mild obrosion ZO CSI ~

'r%, ' , ~ :

'. ~:, j,~ ? ! l

~5o
100

ilOOpml |
oboridloyer (Fe28) 1650HV0,2 I0

50
/

/'

- A~sp =0,2127?

.,I 5Opm chernnicke[composHe Coohng (dlomondporticles) RV 0,2 @I0 5

//
5000
fev

/~msp "0'00727 m-~U

,__..~__~_-.-..-.~
500
rev

1000

10000

Fig. 16. M i l d a n d s e v e r e a b r a s i v e w e a r o f a c h e m i c a l l y d e p o s i t e d c o a t i n g o f n i c k e l a n d d i a m o n d p a r t i c l e s and of a boride layer

142
5. SUMMARIZING REMARKS

E. BROSZEIT

Nickel dispersion coatings containing the dispersoid SiC have acceptable wear properties. Their application is limited, however, with respect to the maximum temperature. A major field of application is the cylinder bore and Wankel trochoid coating for combustion engines. For temperatures above 400C TiC or A120 3 should be used as dispersoids. Further results about the properties of dispersion coatings have been described in detail in refs. 6-14.
ACKNOWLEDGMENT

This work was supported by the Deutsche Forschungsgemeinschaft.

REFERENCES l 2 3 4 5 6 V.P. Greco and W. Baldauf, Plating (East Orange, N J), 55 (1968) 250. P . K . Sinha, N. Dhananjayan and H. K. Chakrabarti, Plating (East Orange, N J), 60 (1973) 1, 55. M. Viswanathan, Met. Finish., 73 (1975) 38. E.C. Kedward, C. A. Addison and A. A. B. Tennett, IMF (Inst. Met. Finish.) Symp. Publ., 54 (1976) 8. W . F . Sharp, Wear, 32 (1975) 315. E. Broszeit, G. Heinke and H. Wiegand, Metall (Berlin), 25 (1971) 470 475. E. Broszeit, G. HeinkeandH. Wiegand, Metall(Berlin),25(1971)lllO 1114. E. Broszeit, F. J. Hess and E. Wagner, Wear, 30 (1974) 311-319. E. Wagner, H. J. Schwalbe and E. Broszeit, Z. WerkstoJJ~ech., 8 (1977) 225-228. K.H. Kloos, E. Wagner and E. Broszeit, Metalloberft6ehe, 32 (1978) 321-328; 384-388. K . H . Kloos, E. Wagner and E. Broszeit, Z. WerkstofJ?ech., 9 (1978) 305-310. E. Wagner and E. Broszeit, Schmiertech. Tribol., 26 (1979) 17 19. E. Wagner and E. Broszeit, Wear, 55 (1979) 235-244. K . H . Kloos, E. Wagner and E. Broszeit, Z. Werkstoff?ech., 11 (1980) 77 82.

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