SIMTech Technical Report (PT/99/002/ST)

Hard Chrome Replacement by HVOF Sprayed Coatings

Aw Poh Koon Tan Boon Hee Michael Taylor Marcus Weston Jimmy Yip

(Surface Technology Group, Process Technology Division, 1999)

Hard Chrome Replacement by HVOF Sprayed Coatings

PT/99/002/ST

BACKGROUND

Hard chrome has been extensively used for many years in applications that require abrasive sliding wear resistance, such as hydraulic cylinders, rotating shafts, aircraft landing gears, bushing pins, pistons, valves, rolls and machines tools. However, the toxicity of the galvanic bath and the hexavalent chromium are environmental problems leading to high waste-disposal costs. Furthermore, the often required post-plate baking and if necessary, the grinding of an unevenly thick chrome layer also add to the cost. Additional disadvantages are the microcrack network due to large internal tensile stresses [1,2], the low deposition rates and the limited corrosion protection of the substrate. In USA and Europe, especially in the aerospace industries, many studies were carried out on High Velocity Oxy-Fuel (HVOF) spray coatings to replace hard chrome plating [3-8]. Typically, WC-Co coating is used due to its excellent wear resistance. However, this coating has lower corrosion resistance as compared to other cermet coatings [7,8]. Therefore, more studies into other cermets coatings have been carried out [7,8]. Other potential hard chrome replacement cermet coatings are WC-Co-Cr, WC-CrCNi and CrC-NiCr. Thermal spray coatings can be designed to meet the requirements of a specific application. Hard chrome coating, by contrast, is used as a general purpose coating where in most circumstances, it does not completely meet all engineering requirements. Therefore, to satisfy a specific set of requirements, an in-depth knowledge of the various coatings properties and performance is essential. 2 OBJECTIVE

HVOF are being used as a replacement for hard chrome. In this project, CrC-NiCr, WC-Co-Cr and WC-CrC-Ni powders will be used for coating development and evaluation. These materials are expected to have better corrosion resistance than the well-known WC-Co coatings. Various critical coating properties such as coating microstructure, phase changes due to thermal processing, adhesion strength to substrate material, corrosion, wear and fatigue tests were tested and compared against hard chrome. 3 METHODOLOGY

Figures 1 to 3 are scanning electron micrographs showing the morphology of the as-received powders. Tables 1 and 2 show the properties of the as-received powders. Coating development was done systematically by Design of Experiments (DOE) approach using the HVOF gun (Miller HV2000). Process optimisation was based on minimum coating porosity, as observed metallographically. The optimised coatings were deposited on various test coupons and specimens for further evaluation. Coating hardness values were determined using a Rockwell hardness tester. Surface roughness was measured using a Talysurf profilometer. X-ray diffraction (XRD) analysis was done to determine the extent of phase transformation of the optimised coatings. Adhesion strength was measured in accordance with ASTM C633 [9] using an Instron universal testing machine. Pin-on-disc wear test based on ASTM G99-90 [10] was conducted using the Universal Wear Tester Machine to rank the abrasive wear-resistance of the coatings. The coated pin was configured to slide against a water-lubricated rotating silicon carbide disk at a constant sliding velocity of 0.4m/s. Fatigue tests were carried out to determine whether the coating process had any effect on the fatigue life of the substrate. Two fatigue testing modes,
1

This project aims to develop a range of cermet coatings to replace hard chrome. Typically, WC-Co coatings applied by

Keywords: Hard chrome; Cermets coatings; Thermal spray; Wear & corrosion; Fatigue

Hard Chrome Replacement by HVOF Sprayed Coatings

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rotating bending (RBFT) and axial fatigue (AFT) were used. The RBFT was done using a Fatigue Dynamics, Model RBF300 HT tester (Figure 4). The specimens were tested at a frequency of 50Hz with a stress ratio of R=-1 (alternating tensile and compressive stresses are equal). The AFT was done using an Instron Model 8801 hydraulic dynamic fatigue tester (Figure 5). Testing was conducted under the Load Control mode at a frequency of 50Hz using a sinusoidal waveform and a stress ratio of R=-1. Electro-chemical testing was used to measure the corrosion rate of coatings by exposing the samples to 3% NaCl solution. Salt spray testing based on ASTM B117 [11] was used to measure the percentage area corroded after a 30-day exposure.

Figure 3. SEM image of WC-CrC-Ni powder

Powder CrC-NiCr WC-Co-Cr WC-CrC-Ni

W C Cr Ni Co 4.0 88.0 8.0 81.3 5.2 4.0 - 9.5 68.0 5.0 21.0 6.0 -

Table 1. Composite of as-received powders

Powder CrC-NiCr WC-Co-Cr WC-CrC-Ni

Size range 15 -53m 10 -53m 10 -53m

Remarks Activated Densified Densified

Table 2. Properties of as-received powders

Figure 1. SEM image of CrC-NiCr powder

Test specimen

Figure 2. SEM image of WC-Co-Cr powder

Figure 4. Rotating Bending Fatigue Testing using a Fatigue Dynamics, Model RBF-300 HT tester

Hard Chrome Replacement by HVOF Sprayed Coatings

PT/99/002/ST

2.5 m

Figure 7. Micrograph of WC-Co-Cr coating

Figure 5. Axial Fatigue Testing using Inston Model 8801 hydraulic dynamic fatigue tester

2.5 m

4 4.1

RESULTS Coatings Properties

Figure 8. Micrograph of WC-CrC-Ni coating

Figures 6 to 8 are micrographs showing microstructures of optimised CrC-NiCr, WC-Co-Cr and WC-CrC-Ni coatings respectively. Their porosities are measured to be 0.5%, 3.0% and 3.95% respectively. Table 3 shows the superficial hardness and surface roughness values of these three assprayed coatings and those of hard chrome as a comparison. These data indicate that the sprayed coatings have similar hardness to hard chrome but are considerably rougher. The roughness in the as-sprayed condition, however, is not an issue because the surfaces are usually ground or machined prior to usage.

Coating CrC-NiCr WC-Co-Cr WC-CrC-Ni Hard Chrome

Hardness (HR15N) 87.94 91.82 91.50 91.20

Surface Roughness 6.853m 6.511m 6.466m 0.178m

Table 3. Hardness and surface roughness of various as-deposited coatings

4.2

XRD Analysis

2.5 m

Figure 6. Micrograph of CrC-NiCr Coating

Figures 9, 10 and 11 show the phase analysis by X-ray diffraction technique. Generally, all optimised coatings retain the phases present in the as-received powder. However, some degree of peak broadening due to thermal processing is discernible, suggesting that the coatings contain some amorphous phases. The amorphism can be reduced by recrystallisation using heat treatment processes [12]. However, the heat treatment (600C for tungsten carbidebased coatings [12]) could result in undesirable substrate properties as the treatment temperature could be closed to

Hard Chrome Replacement by HVOF Sprayed Coatings

PT/99/002/ST

or above the critical temperature of the substrate materials. In most application, however, these coatings require no heat

treatment as thermal spraying is considered as a low heat input coating process.

X-ray Intensity 1800

1600 1400 E 1200 1000 800 600 400 200 0 30 35 40 45 50 B D

A = Cr3O4 B = Cr3C2 D = NiCr E = Cr7C3 F = Cr2O3 E F E Coating B B B B

A
B A D

Powder

55

60

65

70

75

80

2 Figure 9. XRD spectra of CrC-NiCr powder and coating

X-ray Intensity 3500

3000 2500 A 2000 C 1500 1000 500 B B C A A

A = WC B = W2C C = Co3W3C D = CrCo

B D B Coating A A,C

A A

Powder 0 30 35 40 45 50 55 60 65 70 75 80

Figure 10. XRD spectra of WC-Co-Cr powder and coating

Hard Chrome Replacement by HVOF Sprayed Coatings

PT/99/002/ST

X-ray Intensity 1400

1200 B D C A 800 B D,E A

1000

A = WC B = Cr3C2 C = Cr-Ni D = Cr3Ni2 E = Cr23 C6 F = Cr2O3 A,D F Coating A A A

600

400 Powder

200

0 30 35 40 45 50 55 60 65 70 75 80

Figure 11. XRD spectra of WC-CrC-Ni powder and coating

4.3

Wear Testing of stainless steel 316 substrate, HVOF sprayed coating and hard chrome. It is interesting to note that the hard chrome coated samples have a fatigue limit lower than that of the bare substrate. In most engineering applications, designers normally presume that coatings do not affect the fatigue strength of the substrate. Current results show that hard chrome coating reduces fatigue strength by

Figure 12 shows the wear resistance of HVOF sprayed coatings relative to hard chrome. All the four HVOF coatings exhibit better abrasive wear resistant than hard chrome. The tungsten carbide-based cermet coatings are 100 times more abrasive wear resistant than hard chrome. 4.4 Fatigue Testing

Figure 13 shows relative fatigue limits

1000

Relative Wear Rate

100 10 1 0.1 Hard Chrome CrC-NiCr WC-Co-Cr WC-CrC-Ni WC-Co

Type of Coating
Figure 12. Relative abrasive wear resistance of coatings

Hard Chrome Replacement by HVOF Sprayed Coatings

PT/99/002/ST

approximately 2% to 5%, whereas thermal sprayed cermet coatings enhance fatigue strength by approximately 17% to 41%. If coatings are used for dimensional restoration, hard chrome could reduce the components fatigue strength by approximately 12% to 17%. By contrast, HVOF coatings could improve it by approximately 2% to 13%. 4.5 Corrosion Testing

replace hard chrome has been developed. Results suggest that thermal sprayed cermet coatings are suitable candidates to replace hard chrome. Various fatigue tests and abrasive wear tests showed that thermal sprayed coatings outperform hard chrome plating. Although hard chrome have better corrosion properties than thermal sprayed coatings, the latter are capable of providing a high level of corrosion protection to mild steel substrates as demonstrated by salt spray testing. The results also show that each thermal sprayed coating possesses its own set of properties which can be selectively exploited for specific applications. Therefore, judicious selection and design of these coatings can enhance the service life of an engineering component which translates into reduced down-time and maintenance.

Figure 14 and Figure 15 show the electrochemical corrosion and the salt spray corrosion tests results respectively. Both tests show that hard chrome has excellent corrosion resistance. However, comparisons between HVOF coated mild steel and the bare substrate show that HVOF coatings can offer relatively good corrosion protection. 5 CONCLUSIONS

In-house competency in the use and testing of thermal sprayed coatings to

Relative Fatigue Limits

1.50

Rotating Bending Axial Fatigue

1.00

0.50

0.00 Substrate WC Co Cr WC Co Cr CrC NiCr CrC NiCr (Incl. (ExcI. (Incl. (Excl. Coating Coating Coating Coating thickness) thickness) thickness) thickness) Hard Hard Chrome Chrome (IncI. (ExcI. Coating Coating thickness) thickness)

Type of Coating
Figure 13. Relative fatigue life of coatings

Hard Chrome Replacement by HVOF Sprayed Coatings

PT/99/002/ST

0.5

mild steel 47.4 mm/year

0.4

0.3

mm/year
0.2 0.1 0 WC-Co-Cr on Stainless Steel WC-CrC-Ni on Stainless Steel CrC-NiCr on Stainless Steel Unground Hard Unground Hard Ground Hard Chrome on Mild Chrome on Chrome on Mild Steel Stainless Steel Steel Ground Hard Chrome on Stainless Steel Bare Mild Steel Substrate Bare Stainless Steel Substrate

Figure 14. Electrochemical corrosion test results of coatings

100 90 80 70 60
Area of Peel

Area (%)

50 40 30 20 10 0
WC-Co-Cr WC-Co-Cr WC-CrC-Ni WC-CrC-Ni CrC-NiCr on CrC-NiCr on Unground on Mild Steel on Stainless on Mild Steel on Stainless Mild Steel Stainless Hard Steel Steel Steel Chrome on Mild Steel Unground Ground Hard Ground Hard Hard Chrome on Chrome on Chrome on Mild Steel Stainless Stainless Steel Steel Bare Mild Steel Substrate Bare Stainless Steel Substrate

Area of Rust

Figure 15 Percentages area of coupons corroded after exposed to salt fog for 30 days

INDUSTRIAL SIGNIFICANCE

Hard chrome plating is an electrolytic process. The toxicity of the galvanic baths and the hexavalent chromium present serious environmental problems leading to high wastedisposal costs and even regulatory restrictions. Therefore, hard chrome

users will soon need a replacement such as thermal sprayed coatings. Moreover, our research results show that thermal sprayed coatings have the following advantages over hard chrome: Suitable for a wide range of substrates (both metal and nonmetal),
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Hard Chrome Replacement by HVOF Sprayed Coatings

PT/99/002/ST

Faster coating deposition for mid size components, More efficient for localised repair or for localised coating of new components, Wide range of coating materials with specific coating properties to meet the respective demands of the application, and Superior wear and fatigue properties coupled with good protection against corrosion.

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With these attributes, thermal sprayed cermet coatings are expected to find a wide range of application such as: aircraft landing gear components, drill bits and pumping components for oil and gas industry, automotive components and marine engineering components.

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REFERENCES
(1) (2) Dennis J K and Such T E, Nickel nd and Chromium Plating, 2 edition, Butterworths & Co., 1986. Nestler M C et al, HVOF-Spraying Vs Hard Chrome Plating Coating Characteristics And Aircraft Applications, Proceedings of the th 15 International Thermal Spray Conference, 25-29 May 1998, Nice, France, (1998), 1073-1082. Sartwell B D et al, HVOF Thermal Spray Coatings Replace Hard Chrome, Advanced Materials & Processes, V156, No 2, Aug 99, 2528. Rastegar F et al, Alternative to chrome: HVOF cermet coatings for high horse power diesel engines, Surface and Coatings Technology, 90 (1997) 156-163. Rigney R W et al, Component repair and chrome plating replacement with new thermal spray in the United States Navy: Successes and the th future, Proceedings of the 15 ITSC, 25-29 May 1998, Nice, France, ASM International (1998), 975-991. Nestles M C et al, HVOF-spraying Vs. hard chrome plating coating characteristics and aircraft

application, Proceedings of the 15 ITSC, 25-29 May 1998, Nice, France, ASM International (1998), 1073-1078. Marple B R et al, Tungsten carbidebased coatings as alternatives to electrodeposited hard chrome, Proceedings of UTSC99, Dusseldorf, Germany, 17-19 March 1999, DVS, (1999), 123-127. Erning U et al, HVOF coatings for hard-chrome replacement properties and applications, Proceedings of UTSC99, Dusseldorf, Germany, 17-19 March 1999, DVS, (1999), 462-467. ASTM C633, Standard Test Method for Adhesion or Cohesive Strength of Flame-Sprayed Coatings, 652656. ASTM G99-90, Standard Test Method for Wear Testing with Pin on Disk Apparatus, 399-403. ASTM B117-95, Standard Practice for Operating Salt Spray (Fog) Testing Apparatus, 17-24. Steward D A et al, Influence of heat treatment on the abrasive wear behaviour of HVOF sprayed WC-Co coatings, Surface and Coatings Technology, 105 (1998) 13-24.

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