Tribology International 65 (2013) 295302

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Tribology International
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Effect of SiO2 and PTFE additives on dry sliding of NiP electroless coating
D. Gutsev a, M. Antonov b,n, I. Hussainova b, A.Ya. Grigoriev a
a b

Metal-Polymer Research Institute NASB, Gomel, Belarus Department of Materials Engineering, Tallinn University of Technology, 19086 Tallinn, Ehitajate tee 5, Estonia

a r t i c l e i n f o
Article history: Received 3 August 2012 Received in revised form 7 December 2012 Accepted 10 December 2012 Available online 8 January 2013 Keywords: NiP self-lubricating coating SiO2 and PTFE additives Dry sliding Coefcient of friction

abstract
The aim of the present work is to study the effect of silicon dioxide and polytetrauoroethylene (PTFE) additives on NiP coating performance under dry (unlubricated) conditions in unidirectional and reciprocating sliding modes in Ball-on-Flat conguration. Yttria-stabilized zirconia and chrome steel balls were used as counterbodies. Microstructural examination of specimens was conducted by a SEM with EDS. It was found that in contact with steel ball both additives were benecial, while addition of SiO2 particles was detrimental for contact against ceramic ball. The highest improvement of tribological performance was obtained for NiP coated samples having PTFE or mixed additives. & 2013 Elsevier Ltd. All rights reserved.

1. Introduction Nickelbased coatings are widely used in mechanical engineering, electronics and chemical industry because of their hardness, corrosion and wear resistance. Their stable coefcients of friction (COF) in vacuum and air as well as high electrical conductivity make them promising for various applications in many sectors of industry such as transport (air, sea and land), energy generation, and manufacturing [17]. The challenge arises to development of nanostructured coatings that benet from the unique physical and tribological properties of functional layers and nanoparticles incorporated into their structures. Signicant improvement in tribological characteristics of NiP coatings can be reached by introducing self lubricating agent. Nowadays, a successful application of uopolymer nanollers such as polytetrauorethylen (PTFE), peruoroalkoxy (PFA), uorinated ethylene propylene (FEP) and ethylene tetrauoroethylene (ETFE) for reduction wear losses and increase durability of the nal product is of a great interest for industry. These llers are found to increase plasticity of Ni-based matrix and prevent crystallisation of the coating at counterbodies contact spots where the ash temperature caused by frictional heating increases to a great extent. Electroless (chemical) deposition allows obtaining coatings of uniform thickness of any irregularly shaped surfaces made of either metallic or non-metallic materials. A process of deposition

Corresponding author. Tel.: 372 6203355; fax: 372 6203480. E-mail addresses: [email protected], [email protected] (M. Antonov).

is based on oxidationreduction reaction, when reducer is oxi dised by H2PO4 and Ni2 ions are precipitated onto substrate surface [8,9]. Generally there is a linear relationship between a holding time (in bath) and a nal coating thickness [9]. Co-plating of phosphorus (P) results in formation of nickel phosphide (NiP and Ni3P) enabling sufcient increase in hardness of a coating (up to 1000 HV) during heat treatment [1012]. One of the current trends is a process of chemical codeposition of nickel added by hard (ceramic) particles such as SiC, B4C, Cr2C3, WC, BN, Si3N4, Al2O3, ZrO2, TiO2, K2Ti6O13, CeO2, SiO2, diamond [5,6,1318] and carbon nanotubes; or solid lubricants such as PTFE, MoS2, WS2, graphite [4,5,1925], etc. Incorporation of suitable additives results in increasing hardness and wear resistance as well as decreasing coefcient of friction of the coatings that allows service in dry conditions without additional lubricant. By co-depositing the PTFE particles, the hydrophobic coating with excellent anti-sticking performance, and lubricating ability can be obtained. According to authors knowledge the NiP coatings added by combined PTFE and SiO2 particles have not been studied yet. It is supposed that silicon dioxide particles impede dislocation movement and act as barriers to retard the plastic deformation of ductile NiP matrix and hence increase the microhardness while PTFE reduces the COF and increase a load bearing capacity. The aim of the present work is to study the effect of silicon dioxide and polytetrauoroethylene (PTFE) additives on NiP coating performance under dry sliding conditions in unidirectional and reciprocating mode in Ball-on-Flat conguration. The scanning method for the evaluation of the critical forces was applied to improve the differentiation among coatings.

0301-679X/$ - see front matter & 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.triboint.2012.12.012

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2. Materials and methods 2.1. Materials Composite NiP-based coatings with additions of SiO2 and/or PTFE were deposited using electroless nickel bath containing nanosized (520 nm) silicon dioxide (SiO2) particles (GOST 14922) at pH 4.6 7 0.4 and temperature 9095 1C during 1 h. Phosphorus content in the NiP coating was 10 wt%. The coatings (Fig. 1) were deposited onto a mild carbon steel substrate (S235J2G3, EN10025). Concentration of SiO2 particles in the solution was held on the level of 1.5 and 3.0 wt% that resulted in the concentration of silicon dioxide in the coating equal to 4.5 and 7.0 vol% respectively that is lower than reported in Ref. [26]. The amount of the silicon dioxide was conrmed by EDS analysis of polished samples. In general, electroless co-deposition processes of second phase particles take place at low temperature and the chemical interaction is not favoured between the particles and the matrix. The particles are only physically entrapped into the NiP matrix. Therefore heat treatment of these coatings is necessary to promote high hardness and improve wear resistance. Coatings have been heat treated at 400 1C for 1 h [26,27]. Low-molecular ne-dispersed PTFE particles (size of a single particle was not exceeding 7 mm) were sprayed onto the base coating and melted

at 340 1C during 1 h. Thickness of the PTFE layer was nonuniform: it was larger at the place of initial position of the PTFE cluster and less between them (Fig. 1c and d). Coatings compositions and their thicknesses are given in Table 1. The specimens were prepared in size of 5 mm 15 mm 30 mm. The coatings were tested as received without any surface modication. The

Fig. 2. Schematic representation of NiP coating with SiO2 and PTFE (cross section).

Fig. 1. SEM images of surfaces of as-deposited coatings.

Table 1 Properties of the coatings studied. Coating Thickness (mm) Microhardness (HV0.05) Roughness parameters (mm) Ra NiP NiP4.5 vol% SiO2 NiP7.0 vol% SiO2 NiPPTFE NiP4.5 vol% SiO2PTFE NiP7.0 vol% SiO2PTFE Steel substrate (S235J2G3) 6.0 7 1.8 5.0 7 0.7 6.6 7 0.3 4.7 7 0.8 5.7 7 0.1 3.7 7 0.1 812 7 125 849 7 204 946 7 345 543 7 63 50 7 148 593 7 139 232 7 12 1.5 7 0.2 1.5 7 0.2 1.2 7 0.1 1.4 7 0.2 1.4 7 0.3 1.6 7 0.2 1.2 7 0.1 Rmax 12.6 7 1.2 13.0 7 2.8 10.9 7 1.1 13.4 7 3.0 15.7 7 5.8 13.2 7 5.5 9.8 7 1.0 Rz 10.5 7 1.3 10.7 7 1.4 8.8 7 1.4 11.1 7 1.4 10.3 7 3.1 10.6 7 2.5 8.3 7 1.4

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schematic cross-sectional representation of the NiP coating with SiO2 and PTFE is depicted in Fig. 2.

2.2. Experimental details Microstructural examination of specimens was conducted by a scanning electron microscope (SEM) Zeiss EVO MA15 supplied with energy dispersive X-ray spectroscopy (EDS) INCA analyser and Hitachi TM-1000 scanning electron microscopes with EDS module. Coating thickness was determined by means of ball cratering method (kaloMAX, BAQ GmbH) with the help of optical microscope Zeiss Axiovert-25 according to EN1071. Ball of 20 mm in diameter was used with 5 mm diamond slurry. Values given in Table 1 are the average of three measurements. Microhardness was determined with the help of Buehler Micromet-2001 device. Measurements were done by Vickers diamond indenter using load of 0.5 N according to ISO 6507-2005. Seven measurements of each coating were made, maximum and minimum values were ignored and the average of remaining ve values is given in Table 1. Zwick/Roell ZHR 8150 LK Rockwell hardness testing machine and optical microscope Zeiss Axiovert-25 were applied for assessment of coating adhesion to substrate according to CEN/TS 1071-8. Load was 588.6 N (HRA). Roughness of bodies was measured by Mahr perthometer PGK 120 in contact mode.

Tribological sliding tests were done using CETR UMT-2 tribometer. Main conditions of the testing are given in Tables 2 and 3. High purity yttria-stabilized zirconia (95% ZrO2, 5% Y2O3) ceramic balls of hardness HV10 1250 and roughness Ra 0.08 mm as well as steel balls (EN 100Cr6/ AISI 52100 bearing chrome steel) of hardness HV 848 (converted from HRC) and roughness Ra 0.07 mm

Fig. 3. Determination of the critical force by scanning method (step 2).

Table 2 Sliding test conditions with constant load. Parameter Conguration Ball-On-Plate Mode Ball diameter (m) Ball material Load, N (g) Amplitude (m) Radius (circumference) of track (m) Frequency (Hz) Linear velocity, (m s 1) Duration (min) Wear path length (m) Number of repetitive sliding events (motions) other the same point on the track, times Atmosphere
n

Ball-On-Disk unidirectional 3 10 3 ZrO2 and EN 100Cr6 (AISI 52100) 0.98 (100) 5 (31.4) 10 3 0.033 60 120 3822

reciprocating 3 10 3 ZrO2 and EN 100Cr6 (AISI 52100) 0.98 (100) 5 10 3 5 0.050 5 (300n) 15 (900n) 3000 (180,000n)

Air, 23 7 2 1C, relative humidity 45 7 5%

Test with duration of 300 min was performed for NiPPTFE coating to estimate the resistance and to monitor wear mechanism.

Table 3 Scanning test conditions to determine the critical load. Feature/parameter Conguration Mode Ball diameter (m) Ball material Load, N (g) Description Ball-On-Plate, plate is coated Ball is reciprocating, plate is moving, force is increased 3 10 3 EN 100Cr6 (AISI 52100) 0.108.92 (10910) for coatings without PTFE 0.98 - 98.98 (100 - 10100) for PTFE containing coatings 0.49 (50)n 1 10 3 10 10 3 5 50 (1.7) 200 (6.7) 800 (26.7) 3200 (106.7) 12,800 (426.7) Not moving Air, 23 7 2 1C, relative humidity 45 7 5%

Amplitude (m) Length of scan (plate movement) (m) Frequency (Hz) Feed i.e. sample movement rate, cycles mm-1 (duration of test, min)

Atmosphere
n

For determination of the COF used for tracing the critical force (Fig. 3).

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Fig. 4. Evolution of coatings COF under constant load in reciprocative and unidirectional regimes with ZrO2 and 100Cr6 balls.

Fig. 5. Effect of lower specimen feeding rate on critical force for NiP7 vol%SiO2 PTFE coating determined by scanning method.

were used. Prolonged tests were carried out to monitor the wear mechanism. NiP coatings, especially with PTFE additives are having excellent wear resistance and low COF and the tribological test to obtain reliable material loss data would be extremely time consuming. The substrate and coating (NiP coating usually replicate the substrate roughness) were prepared to have roughness (Table 1) being high comparing to that in real applications (Ra 0.12.0 mm). Surfaces with high roughness are used much often since they are easier to produce and they are economically feasible. Coatings have generally better adhesion if they are deposited onto rough surface [4]. However, high roughness leads to generation of extreme stress concentration in the asperities under loading and may result in high wear and low load carrying capacity. In addition to high roughness, coating has a multilayer structure with phases (PTFE, NiP, SiO2; Fig. 2) having different

density, COF and wear rate. PTFE is present only on the top of the coating and it is not reasonable to measure the mass or volume loss of such multilayer coating. It is also noted by other researchers that NiP deposits are too thin for reliable wear rate measurements [4] even for much thicker coatings (35 mm [27], 2530 mm [26]). The scanning test (Table 3, Fig. 3) similar to those used with another tribological devices [28,29] was applied instead to determine the critical load that may be carried by coating. The idea of the method is to move the coated specimen in two directions. Specimen is moving back and forward as during usual reciprocating test (along X axis, amplitude 1 mm, Fig. 3) while at the same time it is continuously and unidirectionally being moved to supply fresh coating into contact (along Y axis, 10 mm). The feed rate is the number of reciprocative cycles done by specimen in X direction while it travels 1 mm in Y direction. Frequency of reciprocation in X direction is same for all tests. High value of feed rate means that the velocity in Y direction is low and the time required to nish test is longer. The test comprises two steps. The rst step is required to obtain COF of the coating in mild conditions with constant force of 0.49 N (feed rate is 800 cycles mm 1) to ensure that the coating is not damaged. The second step is done to determine the maximum critical force that the coating is able to sustain. The only difference between the steps is that during the second step the force is continuously increased from low to high level. The analysis of the second step results are done after the test. When the force is low enough the COF is similar to that observed during the rst step. The force corresponding to the COF that is 50% higher than the COF of the coating determined during the rst step is assumed as a critical one. Fresh surface of coating was used for both steps. At least 3 tests were performed and the average value is calculated. Scanning test was done only with the steel ball that is mostly used as counterbody for NiP coatings.

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Fig. 6. Coefcient of friction and critical forces of coatings tested by scanning method.

3. Results It is evident from Table 1 that there is an increase in the hardness values obtained due to the SiO2 particle reinforcement

in the NiP matrix. It is known that ne precipitations create an additional barrier for the movement of dislocation to propagate. Addition of PTFE droplets results in the lower hardness values as compared to untreated coatings (Table 1). Lower hardness values

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Fig. 7. SEM image of NiPPTFE coating after 300 min reciprocative test (extended duration). PTFE layers are appeared as the dim grey coloured areas (indicated by arrows).

of the samples with NiPTFE and NiP7.0 vol% SiO2PTFE coatings can also be attributed to lower thickness of these coatings and related increased inuence of softer substrate during hardness measurement. Microstructure of NiP-based coatings is composed of characteristic globular shaped grains (Figs. 1, 2). It was found (by EDS) that grain boundaries have higher phosphorus content than grain interiors. Coating with high content of SiO2 (NiP7.0 vol% SiO2) has slightly smaller size of grains, lower roughness and low level of porosity and other defects (outgrowths protruding above the surface, agglomerates having low adhesion with coating, etc.) as compared to base NiP coatings (Fig. 1; Table 1). PTFE clusters of NiPSiO2PTFE coating are shown in Fig. 1(d). Coating with SiO2 has more uniform distribution of PTFE clusters (compare Fig. 1c and d). There is signicant dispersion of thickness measurement results that is associated with high roughness of initial substrates and deposited coatings (Table 1). Roughness of the deposit added by SiO2 is decreased while roughness of the deposit coated by PTFE is slightly increased. Single radial cracks without adhesive delamination were characteristic for all coatings studied that corresponds to the Class 1 according to CEN/TS 1071-8 indicating good adhesion of the coatings to the substrate. Behaviour of the coatings in both modes (reciprocating and unidirectional sliding) is similar (Fig. 4). COF of NiPPTFE and NiPSiO2PTFE coatings was usually improved by additives comparing to the basic NiP coating. Addition of SiO2 (NiP- 7 vol%SiO2 coating) is favourable only when steel ball (100Cr6) is used. When ceramic ball (ZrO2) with hardness exceeding that of the NiPSiO2 coating is used, the SiO2 additives do not prevent the coating from the excessive wear. Wear mechanism in this case could be characterised by growing role of a brittle mode of fracture. Behaviour of coatings during scanning test was similar (comparing to conventional test results), generally resulting in higher value of critical force when sufcient supply of fresh coating material was enabled (low value of feed rate), Fig. 5. The lowest critical force was observed during tests with slow movement of the sample in Y direction (high feed rate) when the contact between the side wall of wear crater and steel ball took place. In conditions when wear debris are accumulated and are serving as solid lubricant (sample is not moving in Y direction) the sufciently high critical force was measured. Critical forces for coatings determined with feed rate of 800, 12,800 cycles mm 1 and when the sample was not moving in Y direction are given in Fig. 6. Addition of PTFE enables to reduce the COF of coatings several times during conventional tests (Fig. 4) and down to 37% when determined by scanning method (Fig. 6). Addition of silicon dioxide was benecial in reduction of the COF only in case of NiP4.5 vol% SiO2PTFE coating. Critical forces of PTFE-containing coatings are order of magnitude higher

than that of plain NiP or NiP with silicon dioxide additives. Plain NiP has higher critical force when the sample is not moving or moving very slowly (high value of feed rate). Addition of SiO2 to NiP is benecial only when supply of fresh coating is sufcient (feed 800 cycles mm 1). Addition of silicon dioxide to the NiP PTFE coating cannot signicantly improve the load bearing capacity of the tribosystem. SEM images after testing of coatings by conventional (Fig. 7) and scanning method (Fig. 8) with results of EDS analysis (Table 4) are showing that the highest peaks of NiP and later that of steel substrate material are rst removed from the surface. Iron is present on the surface even after testing with low force (a1a3, d1, d2, g1, g2; Table 4) that indicates that highest peaks are already worn. In the case of PTFE containing coatings the load is carried by PTFE clusters providing almost no wear for substrate and NiP (Fig. 7). Particles of wear debris (NiP and steel) were found to be embedded into the PTFE clusters (Fig. 7b). Mechanical mixing of components was observed (b4, e3, h2; Table 4). Main mechanism of coatings degradation is adhesive and oxidative wear off at the contact points where high ash temperature is generated. Wear debris are more oxidised than initial coating. Fine wear debris (b4, c2, c3, f5; Table 4) have higher content of oxygen than coarse ones (a3, b3, g5; Table 4). PTFE content (uorine, Table 4) in all locations of PTFE containing coatings was sufciently high indication that it is covering the whole surface. PTFE is transferred even to damaged surface of coating (e4, Table 4) Rapid reduction of PTFE was observed after failure of coatings (f1f5, j1j3; Table 4). Scufng was observed only after failure of the coating when force was higher than critical for given coating.

4. Discussion PTFE addition is benecial if reduced COF and increased critical force are required. This can be explained by formation of the PTFE-rich mechanically mixed layer responsible for good antifriction properties (Figs. 48) [4,30]. SiO2 may be required for long runs in real applications to provide a load-bearing capacity for protection of NiPPTFE containing tribo-layer from shearing. Indeed, silicon dioxide additions were benecial to increase the hardness of the NiP and NiP PTFE coatings. However they are able to reduce the COF for NiP coating only with steel counterbody when tested under low loads (0.98 N, Fig. 4). Critical loads of silicon dioxide containing coatings may be improved only when supply of fresh coating surface is sufcient (Figs. 5, 6). High stresses generated during the contact between ceramic counterbody and silicon dioxide leads to the rupture of the nickel oxide and PTFE lm, direct and fatigue

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Fig. 8. SEM images of NiP, NiPPTFE and NiP7.0 vol% SiO2PTFE coatings after testing by scanning method with indication of force and locations where EDS analysis was performed (see also Table 4).

crashing and removal of the silicon dioxide that starts acting as an abrasive that in its turn leads to higher wear rates. Similar signicant reduction of wear resistance was also observed in the case of NiPPTFE coating sliding in air and in nitrogen atmosphere [31] when the formation of nickel oxide layer was impeded.

5. Conclusions 1. PTFE addition reduces coefcient of friction and increases load carrying capacity of NiP coating when rubbed against ceramic or steel counterbody.

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Table 4 Results of EDS analysis of worn surfaces of coatings. Locations are depicted in Fig. 8. Coating Position Elements (wt%) Ni NiP a1 a2 a3 b1 b2 b3 b4 c1 c2 c3 c4 d1 d2 e1 e2 e3 e4 e5 f1 f2 f3 f4 f5 g1 g2 g3 g4 g5 h1 h2 i1 i2 i3 j1 j2 j3 83.1 85.2 77.3 85.6 84.9 72.8 52.5 81.0 51.2 52.7 2.9 82.2 29.5 82.0 81.8 49.8 55.2 69.4 0.1 2.5 0.5 3.0 1.3 78.7 80.7 64.5 80.4 68.0 72.2 39.5 30.2 77.5 62.9 15.2 4.5 3.6 P 12.7 11.5 11.2 10.4 11.8 10.6 8.7 11.0 8.0 8.3 0.4 12.1 2.8 12.7 12.0 5.5 10.3 10.7 0.1 0.4 0.2 0.5 0.2 10.8 12.5 3.3 11.5 9.6 9.8 6.2 2.6 10.3 8.5 2.2 0.5 0.6 F 2.9 95.5 1.9 2.2 40.8 15.9 2.0 0.7 0.0 0.8 0.0 0.0 2.8 1.8 27.7 2.1 11.2 3.1 15.1 2.2 2.3 3.0 1.3 0.8 0.8 Si 0.8 0.7 0.3 0.5 1.9 0.7 1.2 0.2 0.5 0.6 0.1 0.1 0.0 O 2.0 1.4 8.4 1.3 0.9 5.5 31.3 3.1 24.2 26.2 2.7 1.3 0.8 0.5 2.1 1.1 2.1 2.5 1.1 22.1 8.5 16.6 30.4 3.4 1.5 1.3 1.8 6.0 6.0 19.4 5.7 4.1 4.3 4.9 7.5 4.6 Fe 2.2 2.0 3.1 2.7 2.4 11.1 7.4 4.9 16.7 12.8 94.0 1.6 1.3 2.9 2.0 2.4 16.5 15.5 98.0 75.0 90.1 80.0 68.1 3.6 2.9 2.8 3.9 3.4 8.3 18.6 59.2 5.3 20.8 76.4 86.7 90.3

NiPPTFE

NiP7.0 vol% SiO2PTFE

2. Addition of silicon dioxide to NiP is benecial only in the case of steel counterbody under low loads or with sufcient supply of fresh coating material into contact zone. 3. Nano-sized SiO2 addition to NiP coating slightly reduces the size of grains and roughness. 4. Method for determination of the load carrying capacity (critical force) of the thin coatings in Ball-On-Plate conguration is proposed.

Acknowledgements The authors would like to acknowledge DoRa programme (personal grant for D.Gutsev) as well as Estonian Ministry of Education and Research (Targeted nance Project no. SF0140062s08) and Estonian Science Foundation (grants ETF 8850 and 8211) for the nancial support of the study. References
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