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<a href=Wear 311 (2014) 101 113 Contents lists available at S c i e n c e D i r e c t Wear journal homepage: w w w . e l s e v i e r . c o m / l o c a t e / w e a r Wear studies on plasma sprayed Al O – 40 wt% 8YSZ composite ceramic coating on Ti – 6Al – 4V alloy used for biomedical applications G. Perumal , M. Geetha , R. Asokamani , N. Alagumurthi V.R.S. College of Engineering and Technology, Arasur, Villupuram 607107, Tamil Nadu, India Centre for Biomaterials Science and Technology, School of Mechanical and Building Sciences, VIT University, Vellore 632014, Tamil Nadu, India Dhanalakshmi College of Engineering, Anna University, Chennai 601301, Tamil Nadu, India Pondicherry Engineering College, Pondicherry 605104, India article info Article history: Received 13 October 2013 Received in revised form 31 December 2013 Accepted 31 December 2013 Available online 9 January 2014 Keywords: Thermal spray coatings Scratch testing Sliding wear Joint prostheses abstract The relative wear resistance of three candidate coatings for titanium alloy-based orthopedic applications was compared using a reciprocating test method. Micrometer-sized powders of the following composi- tions were plasma sprayed onto Ti – 6Al – 4V (TAV) alloy: (i) Al O (AO), (ii) 8 mol% yttria stabilized zirconia (8YSZ) and (iii) Al O – 40 wt% 8YSZ (A4Z). Deposits were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and porosity measurements. In addition, microindentation hard- ness measurements and scratch-based adhesive/cohesive strength measurements were also performed. The composite coating (A4Z) had superior wear resistance. Wear track examination suggests two reasons for this improvement. First, the A4Z coating had improved cohesive strength between splats, and second, there was a phase transition toughening mechanism associated with tetragonal zirconia. Results of contact mechanics calculations support the experimental fi ndings. & 2014 Elsevier B.V. All rights reserved. 1. Introduction Ti – 6Al – 4V alloys are found to be increasingly used in load bearing bio-implants due to their advantageous properties such as low density, high strength to weight ratio, greater corrosion resis- tance and excellent biocompatibility. The other added advantage of Ti alloy is its modulus of elasticity (113 GPa) which is closer to that of bone (30 GPa), compared to that of other conventional alloys such as 316 stainless steel and Co – Cr whose modulii of elasticity are 210 GPa and 240 GPa and it should be noted that the lower modulii results in the decrease of the stress shielding effect which in turn leads to enhanced service period. However, poor tribological properties of Ti alloys restrict their usage for articulating devices used in biomedical fi eld. The alloy Ti – 6Al – 4V has been widely used despite concerns in the medical community that Al might be carcinogenic and that V might lead to Alzheimer disease. This eventually led to the usage of II/III generation alloys such as V free Ti – 6Al – 7Nb and further several low modulus beta titanium alloys with non-toxic alloying elements have been developed and extensively investigated by several researchers all over the world. The metallurgical aspects and biocompatibility issues of different Ti alloys have been discussed in detail in the review article written by two of the authors of the present paper [1] . Amongst different beta titanium alloys, TNZT and Corresponding author. Tel.: þ 91 9840896296. E-mail addresses: perumal_harish@yahoo.com (G. Perumal), gmv1225@yahoo.com , geethamanivasagam@vit.ac.in (M. Geetha), asokamanir@yahoo.co.uk (R. Asokamani), alagu_pec@yahoo.co.in (N. Alagumurthi). 0043-1648/$ - see front matter & 2014 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.wear.2013.12.027 Ti – 13Nb – 13Zr alloys have received greater attention and cataloged under ASTM. In spite of the fact that certain issues related to Ti – 6Al – 4V implant are still relevant, several major manufacturers of implants continue to offer Ti – 6Al – 4V alloy to develop orthopedic implants. Hence, in this study we have attempted the coatings on the most widely used Ti – 6Al – 4V implant with the aim of choosing the best coating which has higher wear resistance. Currently, ceramic materials are considered to be an alternative for metal – polyethylene based implants or metal – metal articulating devices due to their unique features of high hardness, superior tribological performance along with the excellent biocompatibility. Further, the recent works in this area reveals that, the wear rates are reduced signi fi cantly when ceramic femoral head is made to move either over polyethylene or ceramic cup [2 – 7] . Though many previous works have reported that Al O and ZrO ceramic materials have withstood the harsh environment in the human body, brittle- ness and low fracture toughness of pure alumina and hydrothermal instability of zirconia implants limit their usage for biomaterial implants [9,10] and therefore more recently alumina – zirconia toughened composites have been proposed for the fabrication of the acetabular cup and femoral heads, as they provide the superior combination of mechanical properties and wear resistance. The increase in the fracture toughness of these composites is attributed to the presence of zirconia as the fracture strength of zirconia ceramic is approximately double that of alumina and the enhanced tribological properties due to the addition of hard alumina [3,8] . Hip simulator experiments carried out on different compositions of alumina – zirconia (ranging from 0% to 80%) clearly demonstrated " id="pdf-obj-0-7" src="pdf-obj-0-7.jpg">

Contents lists available at ScienceDirect

Wear

journal homepage: www.elsevier.com/locate/wear

<a href=Wear 311 (2014) 101 113 Contents lists available at S c i e n c e D i r e c t Wear journal homepage: w w w . e l s e v i e r . c o m / l o c a t e / w e a r Wear studies on plasma sprayed Al O – 40 wt% 8YSZ composite ceramic coating on Ti – 6Al – 4V alloy used for biomedical applications G. Perumal , M. Geetha , R. Asokamani , N. Alagumurthi V.R.S. College of Engineering and Technology, Arasur, Villupuram 607107, Tamil Nadu, India Centre for Biomaterials Science and Technology, School of Mechanical and Building Sciences, VIT University, Vellore 632014, Tamil Nadu, India Dhanalakshmi College of Engineering, Anna University, Chennai 601301, Tamil Nadu, India Pondicherry Engineering College, Pondicherry 605104, India article info Article history: Received 13 October 2013 Received in revised form 31 December 2013 Accepted 31 December 2013 Available online 9 January 2014 Keywords: Thermal spray coatings Scratch testing Sliding wear Joint prostheses abstract The relative wear resistance of three candidate coatings for titanium alloy-based orthopedic applications was compared using a reciprocating test method. Micrometer-sized powders of the following composi- tions were plasma sprayed onto Ti – 6Al – 4V (TAV) alloy: (i) Al O (AO), (ii) 8 mol% yttria stabilized zirconia (8YSZ) and (iii) Al O – 40 wt% 8YSZ (A4Z). Deposits were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and porosity measurements. In addition, microindentation hard- ness measurements and scratch-based adhesive/cohesive strength measurements were also performed. The composite coating (A4Z) had superior wear resistance. Wear track examination suggests two reasons for this improvement. First, the A4Z coating had improved cohesive strength between splats, and second, there was a phase transition toughening mechanism associated with tetragonal zirconia. Results of contact mechanics calculations support the experimental fi ndings. & 2014 Elsevier B.V. All rights reserved. 1. Introduction Ti – 6Al – 4V alloys are found to be increasingly used in load bearing bio-implants due to their advantageous properties such as low density, high strength to weight ratio, greater corrosion resis- tance and excellent biocompatibility. The other added advantage of Ti alloy is its modulus of elasticity (113 GPa) which is closer to that of bone (30 GPa), compared to that of other conventional alloys such as 316 stainless steel and Co – Cr whose modulii of elasticity are 210 GPa and 240 GPa and it should be noted that the lower modulii results in the decrease of the stress shielding effect which in turn leads to enhanced service period. However, poor tribological properties of Ti alloys restrict their usage for articulating devices used in biomedical fi eld. The alloy Ti – 6Al – 4V has been widely used despite concerns in the medical community that Al might be carcinogenic and that V might lead to Alzheimer disease. This eventually led to the usage of II/III generation alloys such as V free Ti – 6Al – 7Nb and further several low modulus beta titanium alloys with non-toxic alloying elements have been developed and extensively investigated by several researchers all over the world. The metallurgical aspects and biocompatibility issues of different Ti alloys have been discussed in detail in the review article written by two of the authors of the present paper [1] . Amongst different beta titanium alloys, TNZT and Corresponding author. Tel.: þ 91 9840896296. E-mail addresses: perumal_harish@yahoo.com (G. Perumal), gmv1225@yahoo.com , geethamanivasagam@vit.ac.in (M. Geetha), asokamanir@yahoo.co.uk (R. Asokamani), alagu_pec@yahoo.co.in (N. Alagumurthi). 0043-1648/$ - see front matter & 2014 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.wear.2013.12.027 Ti – 13Nb – 13Zr alloys have received greater attention and cataloged under ASTM. In spite of the fact that certain issues related to Ti – 6Al – 4V implant are still relevant, several major manufacturers of implants continue to offer Ti – 6Al – 4V alloy to develop orthopedic implants. Hence, in this study we have attempted the coatings on the most widely used Ti – 6Al – 4V implant with the aim of choosing the best coating which has higher wear resistance. Currently, ceramic materials are considered to be an alternative for metal – polyethylene based implants or metal – metal articulating devices due to their unique features of high hardness, superior tribological performance along with the excellent biocompatibility. Further, the recent works in this area reveals that, the wear rates are reduced signi fi cantly when ceramic femoral head is made to move either over polyethylene or ceramic cup [2 – 7] . Though many previous works have reported that Al O and ZrO ceramic materials have withstood the harsh environment in the human body, brittle- ness and low fracture toughness of pure alumina and hydrothermal instability of zirconia implants limit their usage for biomaterial implants [9,10] and therefore more recently alumina – zirconia toughened composites have been proposed for the fabrication of the acetabular cup and femoral heads, as they provide the superior combination of mechanical properties and wear resistance. The increase in the fracture toughness of these composites is attributed to the presence of zirconia as the fracture strength of zirconia ceramic is approximately double that of alumina and the enhanced tribological properties due to the addition of hard alumina [3,8] . Hip simulator experiments carried out on different compositions of alumina – zirconia (ranging from 0% to 80%) clearly demonstrated " id="pdf-obj-0-57" src="pdf-obj-0-57.jpg">

Wear studies on plasma sprayed Al 2 O 3 40 wt% 8YSZ composite ceramic coating on Ti6Al 4V alloy used for biomedical applications

<a href=Wear 311 (2014) 101 113 Contents lists available at S c i e n c e D i r e c t Wear journal homepage: w w w . e l s e v i e r . c o m / l o c a t e / w e a r Wear studies on plasma sprayed Al O – 40 wt% 8YSZ composite ceramic coating on Ti – 6Al – 4V alloy used for biomedical applications G. Perumal , M. Geetha , R. Asokamani , N. Alagumurthi V.R.S. College of Engineering and Technology, Arasur, Villupuram 607107, Tamil Nadu, India Centre for Biomaterials Science and Technology, School of Mechanical and Building Sciences, VIT University, Vellore 632014, Tamil Nadu, India Dhanalakshmi College of Engineering, Anna University, Chennai 601301, Tamil Nadu, India Pondicherry Engineering College, Pondicherry 605104, India article info Article history: Received 13 October 2013 Received in revised form 31 December 2013 Accepted 31 December 2013 Available online 9 January 2014 Keywords: Thermal spray coatings Scratch testing Sliding wear Joint prostheses abstract The relative wear resistance of three candidate coatings for titanium alloy-based orthopedic applications was compared using a reciprocating test method. Micrometer-sized powders of the following composi- tions were plasma sprayed onto Ti – 6Al – 4V (TAV) alloy: (i) Al O (AO), (ii) 8 mol% yttria stabilized zirconia (8YSZ) and (iii) Al O – 40 wt% 8YSZ (A4Z). Deposits were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and porosity measurements. In addition, microindentation hard- ness measurements and scratch-based adhesive/cohesive strength measurements were also performed. The composite coating (A4Z) had superior wear resistance. Wear track examination suggests two reasons for this improvement. First, the A4Z coating had improved cohesive strength between splats, and second, there was a phase transition toughening mechanism associated with tetragonal zirconia. Results of contact mechanics calculations support the experimental fi ndings. & 2014 Elsevier B.V. All rights reserved. 1. Introduction Ti – 6Al – 4V alloys are found to be increasingly used in load bearing bio-implants due to their advantageous properties such as low density, high strength to weight ratio, greater corrosion resis- tance and excellent biocompatibility. The other added advantage of Ti alloy is its modulus of elasticity (113 GPa) which is closer to that of bone (30 GPa), compared to that of other conventional alloys such as 316 stainless steel and Co – Cr whose modulii of elasticity are 210 GPa and 240 GPa and it should be noted that the lower modulii results in the decrease of the stress shielding effect which in turn leads to enhanced service period. However, poor tribological properties of Ti alloys restrict their usage for articulating devices used in biomedical fi eld. The alloy Ti – 6Al – 4V has been widely used despite concerns in the medical community that Al might be carcinogenic and that V might lead to Alzheimer disease. This eventually led to the usage of II/III generation alloys such as V free Ti – 6Al – 7Nb and further several low modulus beta titanium alloys with non-toxic alloying elements have been developed and extensively investigated by several researchers all over the world. The metallurgical aspects and biocompatibility issues of different Ti alloys have been discussed in detail in the review article written by two of the authors of the present paper [1] . Amongst different beta titanium alloys, TNZT and Corresponding author. Tel.: þ 91 9840896296. E-mail addresses: perumal_harish@yahoo.com (G. Perumal), gmv1225@yahoo.com , geethamanivasagam@vit.ac.in (M. Geetha), asokamanir@yahoo.co.uk (R. Asokamani), alagu_pec@yahoo.co.in (N. Alagumurthi). 0043-1648/$ - see front matter & 2014 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.wear.2013.12.027 Ti – 13Nb – 13Zr alloys have received greater attention and cataloged under ASTM. In spite of the fact that certain issues related to Ti – 6Al – 4V implant are still relevant, several major manufacturers of implants continue to offer Ti – 6Al – 4V alloy to develop orthopedic implants. Hence, in this study we have attempted the coatings on the most widely used Ti – 6Al – 4V implant with the aim of choosing the best coating which has higher wear resistance. Currently, ceramic materials are considered to be an alternative for metal – polyethylene based implants or metal – metal articulating devices due to their unique features of high hardness, superior tribological performance along with the excellent biocompatibility. Further, the recent works in this area reveals that, the wear rates are reduced signi fi cantly when ceramic femoral head is made to move either over polyethylene or ceramic cup [2 – 7] . Though many previous works have reported that Al O and ZrO ceramic materials have withstood the harsh environment in the human body, brittle- ness and low fracture toughness of pure alumina and hydrothermal instability of zirconia implants limit their usage for biomaterial implants [9,10] and therefore more recently alumina – zirconia toughened composites have been proposed for the fabrication of the acetabular cup and femoral heads, as they provide the superior combination of mechanical properties and wear resistance. The increase in the fracture toughness of these composites is attributed to the presence of zirconia as the fracture strength of zirconia ceramic is approximately double that of alumina and the enhanced tribological properties due to the addition of hard alumina [3,8] . Hip simulator experiments carried out on different compositions of alumina – zirconia (ranging from 0% to 80%) clearly demonstrated " id="pdf-obj-0-71" src="pdf-obj-0-71.jpg">

G. Perumal a , M. Geetha b ,n , R. Asokamani c , N. Alagumurthi d

a V.R.S. College of Engineering and Technology, Arasur, Villupuram 607107, Tamil Nadu, India b Centre for Biomaterials Science and Technology, School of Mechanical and Building Sciences, VIT University, Vellore 632014, Tamil Nadu, India c Dhanalakshmi College of Engineering, Anna University, Chennai 601301, Tamil Nadu, India d Pondicherry Engineering College, Pondicherry 605104, India

article info

Article history:

Received 13 October 2013 Received in revised form 31 December 2013 Accepted 31 December 2013 Available online 9 January 2014

Keywords:

Thermal spray coatings

Scratch testing

Sliding wear

Joint prostheses

abstract

The relative wear resistance of three candidate coatings for titanium alloy-based orthopedic applications was compared using a reciprocating test method. Micrometer-sized powders of the following composi- tions were plasma sprayed onto Ti6Al4V (TAV) alloy: (i) Al 2 O 3 (AO), (ii) 8 mol% yttria stabilized zirconia (8YSZ) and (iii) Al 2 O 3 40 wt% 8YSZ (A4Z). Deposits were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and porosity measurements. In addition, microindentation hard-

ness measurements and scratch-based adhesive/cohesive strength measurements were also performed. The composite coating (A4Z) had superior wear resistance. Wear track examination suggests two reasons for this improvement. First, the A4Z coating had improved cohesive strength between splats, and second, there was a phase transition toughening mechanism associated with tetragonal zirconia. Results of contact mechanics calculations support the experimental ndings. & 2014 Elsevier B.V. All rights reserved.

1. Introduction

Ti6Al4V alloys are found to be increasingly used in load bearing bio-implants due to their advantageous properties such as low density, high strength to weight ratio, greater corrosion resis- tance and excellent biocompatibility. The other added advantage of Ti alloy is its modulus of elasticity (113 GPa) which is closer to that of bone (30 GPa), compared to that of other conventional alloys such as 316 stainless steel and CoCr whose modulii of elasticity are 210 GPa and 240 GPa and it should be noted that the lower modulii results in the decrease of the stress shielding effect which in turn leads to enhanced service period. However, poor tribological properties of Ti alloys restrict their usage for articulating devices used in biomedical eld. The alloy Ti6Al4V has been widely used despite concerns in the medical community that Al might be carcinogenic and that V might lead to Alzheimer disease. This eventually led to the usage of II/III generation alloys such as V free Ti6Al7Nb and further several low modulus beta titanium alloys with non-toxic alloying elements have been developed and extensively investigated by several researchers all over the world. The metallurgical aspects and biocompatibility issues of different Ti alloys have been discussed in detail in the review article written by two of the authors of the present paper [1]. Amongst different beta titanium alloys, TNZT and

n Corresponding author. Tel.: þ 91 9840896296. E-mail addresses: perumal_harish@yahoo.com (G. Perumal), gmv1225@yahoo.com, geethamanivasagam@vit.ac.in (M. Geetha), asokamanir@yahoo.co.uk (R. Asokamani), alagu_pec@yahoo.co.in (N. Alagumurthi).

0043-1648/$ - see front matter & 2014 Elsevier B.V. All rights reserved.

Ti13Nb13Zr alloys have received greater attention and cataloged under ASTM. In spite of the fact that certain issues related to Ti6Al4V implant are still relevant, several major manufacturers of implants continue to offer Ti6Al4V alloy to develop orthopedic implants. Hence, in this study we have attempted the coatings on the most widely used Ti6Al4V implant with the aim of choosing the best coating which has higher wear resistance. Currently, ceramic materials are considered to be an alternative for metalpolyethylene based implants or metalmetal articulating devices due to their unique features of high hardness, superior tribological performance along with the excellent biocompatibility. Further, the recent works in this area reveals that, the wear rates are reduced signicantly when ceramic femoral head is made to move either over polyethylene or ceramic cup [27]. Though many previous works have reported that Al 2 O 3 and ZrO 2 ceramic materials have withstood the harsh environment in the human body, brittle- ness and low fracture toughness of pure alumina and hydrothermal instability of zirconia implants limit their usage for biomaterial implants [9,10] and therefore more recently aluminazirconia toughened composites have been proposed for the fabrication of the acetabular cup and femoral heads, as they provide the superior combination of mechanical properties and wear resistance. The increase in the fracture toughness of these composites is attributed to the presence of zirconia as the fracture strength of zirconia ceramic is approximately double that of alumina and the enhanced tribological properties due to the addition of hard alumina [3,8]. Hip simulator experiments carried out on different compositions of aluminazirconia (ranging from 0% to 80%) clearly demonstrated

102

G. Perumal et al. / Wear 311 (2014) 101 113

that aluminazirconia ceramic cup and ball offer the highest wear resistance with enhanced mechanical properties than pure alumina [3]. However, susceptibility to slow crack growth, squeaking noises, stripe wear and headneck taper mismatching are the major concerns in ceramic-on-ceramic articulating devices [9,10]. Ceramic coatings on implant materials using different surface modication techniques are considered to be alternative solutions to overcome failure of bulk ceramic materials. TiN, DLC and oxide coatings have been attempted using techniques such as ion implantation, PVD, CVD etc. [1114]. However, thin layers formed using these techniques is one of the major disadvantages as they wear out with time. Amongst the different surface modication techniques, plasma spraying which can deposit thick ceramic coating with faster deposition rate is considered to be the highly efcient technique by industries to develop different kinds of hard and soft coatings to prevent the substrate from various surface degradations. Espe- cially in the eld of aerospace, and navy, thermal sprayed coatings are very much utilized as they provide high wear resistance to the substrate material that possesses superior combination of mechanical properties like ductility and strength [15]. Plasma- spraying has also been advocated to develop bio-ceramic (Hydro- xyapatite-HAp) coating on Ti based implants to enhance osseoin- tegration [16,17] and has also been approved by Food and Drug Administration (FDA), USA, for coatings on joint prostheses [18]. However, it is also well known that HAp coating on TAV is not the right combination as the coating does not get adhere well with the substrate due to mismatch in thermal expansion coefcient and this has been studied in greater detail [2628]. Amongst the different ceramic powders that are considered for developing wear resistant coatings, several studies have revealed that the microhardness, toughness, and wear resistance of the Al 2 O 3 coatings can be further improved by the addition of other oxides like ZrO 2 or TiO 2 [1924]. Especially, there are many reports which indicate that Al 2 O 3 coatings with 40 wt% ZrO 2 on steel and stainless steel substrate developed by plasma spray process yields better tribological results which has made us to choose such a coating in the present study [19,22,23]. Though, nanostructured coatings have become an emerging technique, the associated challenging problems such as (i) agglomeration of individual nanoparticles into micron sized particles, (ii) careful control of particle temperature in the plasma jet in order to develop bimodal microstructure [25] and (iii) variation in coefcient of thermal expansion of nanomaterials and micron sized materials have led us to choose micron sized powders for this present work. To the best of the authors 0 knowledge, even though alumina with ZrO 2 has been tried to develop ceramic balls, coating of this combination of ceramic powders on TAV alloy has not been carried out so far for biomedical load-bearing applications. Hence, in the present work an attempt has been made to make use of the advantageous properties of Al 2 O 3 40 wt% ZrO 2 ceramics and develop a composite coating on TAV alloy using atmospheric plasma spraying process for articial hip prostheses and to investigate their tribological properties in simulated body uid environment. In addition, the coating parameters optimized in this study for plasma spraying of ceramic powders is applicable for any Ti alloy. This work was carried out in order to understand the effects of the novel ceramic composite composition proposed in this study on the tribological behavior of Ti alloy.

  • 2. Experimental methods

    • 2.1. Materials and processing

Commercially available Al 2 O 3 with particle size 545 μm and 8 mol% yttria stabilized ZrO 2 with the same particle size as that of

Table 1

Plasma spray parameters of the feedstock.

Parameters

Al 2 O 3

8YSZ

A4Z (composite)

Current (A) Voltage (V) Primary (Ar) gas ow rate (l/min) Secondary (H 2 ) gas ow rate (l/min) Spray distance (mm) Powder feed rate (g/min) Carrier gas ow rate (l/min)

490

70

42

7.2

100

7

5

510

70

42

7.2

100

7

5

550

70

42

6.5

100

9

5

Al 2 O 3 were used to obtain the composite feed stock powders. The as-received Al 2 O 3 powders (fused and crushed) are angular and with irregular shapes, whereas the 8YSZ powders (sintered and agglomerated) are of spherical morphology. Composite feed stock

powder was obtained by blending 60% of Al 2 O 3 and 40% of 8YSZ (by weight) powders using planetary ball mill at a speed of

200 rpm for

the duration of 3 h. Metco 3MB plasma gun with

  • 40 KW atmospheric plasma spray system was used to develop the

coatings as was done in our earlier studies [30]. All the coatings were deposited on biomedical grade Ti6Al4V sample of size

  • 30 30 3 mm 3 using the optimized parameters, which were

obtained after conducting several experiments with different processing parameters. The parameters employed in the present study which led to thick, dense and adherent coatings are given in

Table 1. Before the deposition, the substrate was sand blasted using corundum of size # 24 meshes at an air pressure of about

  • 50 psi.

    • 2.2. Characterization

Surface morphology of all the feed stock powders and as- sprayed coatings were investigated using scanning electron micro- scope (Hitachi, S-3400N). Surface morphology of the coated surfaces as well as cross section was investigated using both optical and scanning electron microscope. For the microstructural investigation, the samples were mounted using bakelite powder and then polished using SiC papers of grit sizes ranging from 120 μm to 1600 μm and followed by mirror polishing with dia- mond paste of size 1 μm. Phase analysis of the feed stock powders and the as-sprayed coatings were performed using X-ray diffractrometer (Brucker, D8

Advance) with Cu Kα radiation. The current and voltage were set at

  • 40 kV and 20 mA and all the readings were collected in the 2θ

ranges from 101 to 901 in a step scan mode with a step of 21/min. Vickers microhardness tester was used to nd the microindenta- tion hardness of the coatings. Microindentation hardness values were was measured across the polished cross-section of the coated samples using a load of 200 g for 15 s and the hardness were measured at ten different points and its average value is reported. Porosity measurements were performed on the cross section of the coatings at seven different areas using the optical microscope (Carl Zeiss, Canada) attached with clemex image analyzer.

  • 2.3. Scratch testing for evaluating adhesion/cohesion strength

The scratch test was performed on the surface of the coatings to determine the cohesion/adhesion strength using microscratch tester (DUCOM, India). Scratch test which is commonly used to determine the adhesion strength of thin coatings is used here to determine the cohesion strength of thick coatings. The load at which the coating fails usually determines the adhesion strength of the coating, while the cohesion strength is determined by observing the failure within the coating after the scratch test using optical microscope [31,32]. In the present study, Rockwell

G. Perumal et al. / Wear 311 (2014) 101 113

103

diamond stylus of radius 200 μm was made to slide over the coatings under ramp loading which ranges from 1 to 100 N at a rate of 10 N/mm with a sliding speed of 0.5 mm/s. After the scratch testing, the onset of coating failure/damage (critical load) as well as the scratch track at the end of load was observed using optical microscope in order to determine the load at which failure occurred and to identify the failure modes respectively. Cohesion strength of the coating was assessed using the method followed by Hawthorne et al. [32], who found that the scratch track width, length of tensile cracking and minimum load at which failure of the coating occurs to be the good indicators to assess cohesion strength.

  • 2.4. Friction and wear test

In the present work wear test was carried out using ball-on plate reciprocating wear tester (TR-285M DUCOM, India) con- structed in accordance with the provision prescribed by ASTM G133 standard. Though, ASTM G133 standard was not intended for screening of bio-implant materials, most of the researchers have followed the ASTM G133 standard for screening the implant materials with different load, stroke length and test duration other than that prescribed by procedure A or B of the standard [3335,48] as an initial screening test for the selection of materials or coatings. Further, as far as the selection of the load is concerned, it has been done on the basis of theoretical calculation made by comparing the contact pressure on femoral head and contact pressure on ball in the ball-on-plate con guration. The calculation was made using the procedure followed by Chikarakara [36]. In addition, it is found that the contact stress on ball due to selected load is higher than the maximum contact stress prescribed by the ASTM F-732 standard (3.54 MPa) which has been specically used for polymeric materials used in the case of total joint prostheses. All the wear experiments were performed with 5 mm diameter Al 2 O 3 ball as a counterpart and the coated Ti6Al4V alloy of dimension 20 mm 20 mm 3 mm as the substrate. Wear test was conducted for the duration of 1,00,000 cycles at a constant load of 10 N at a frequency of 2 Hz with sliding stroke of 15 mm [30,48]. All the wear tests were performed in Hank 0 s solution environment at 37 1C and the constituents of Hank 0 s solution are presented elsewhere [30]. Before the wear test, the coatings were ground using 1600 grit SiC papers and then polished using diamond slurry of size 1 μm.The wear experiment was conducted thrice and the mean weight loss of the ball and the coating were noted. Both the weight loss method and volume loss method were used to calculate the wear rate of the ball and the coatings. In the case of weight loss method, wear rate of the ball and coatings are calculated by the equation given by Adel et al. [37].

Wear rate ¼

W 1 W 2 Sliding distance g=cm

ð1Þ

where, W 1 and W 2 are the weights of the ball or coating before and after the wear test respectively. The weights of the coatings before

Table 2

Phase transition temperature and structure of coating materials.

and after the wear test were determined using electronic weighing balance which has an accuracy of 7 0.0001 g.

The Klaffke 0 s empirical equation [38] which was used to calculate wear volume of the ball is given below,

  • V ¼ Wear volume ¼

d

av

8R

π d av

8

4A

þ

3

mm 3

ð2Þ

where, d av is the average transverse diameter of worn surface of the ball, A is the half of the stroke length and R corresponds to the radius of the ball used. The volume loss of the coating is calculated according to ASTM G133 standard, which is given as

V ¼ AL mm 3

ð3Þ

where, A is the average cross sectional area of the wear track and L is the stroke length. Wear track of all the coatings and balls were also examined using scanning electron microscope to identify the wear mechanism.

  • 3. Results and discussion

    • 3.1. Characterization-phase analysis

The objective of performing the XRD studies on the coatings is to observe the possible phase transformations which would have been undergone by the particles as they are taken to the molten state and quenched during the plasma spray process, which will obviously have a strong bearing on the mechanical properties of the coatings. Table 2 presents the phases of the powders at different temperatures and Fig. 1 shows the XRD patterns of both the as-received feed stock powders and as-sprayed coatings. The XRD study of Al 2 O 3 feed stocks clearly revealed (Fig. 1a) the presence of α-Al 2 O 3 phase, while the XRD pattern of as-sprayed Al 2 O 3 coating (Fig. 1d) reveals the presence of the two forms of

G. Perumal et al. / Wear 311 (2014) 101 – 113 103 diamond stylus of radius

Fig. 1. XRD pattern of as received powder of (a) Al 2 O 3 , (b) 8YSZ, (c) A4Z composite and as-sprayed coatings of (d) Al 2 O 3 , (e) 8YSZ and (f) A4Z composite.

Material

Melting point (1C)

Phases

Phase transition temperature (1C)

Crystal structure

Ref

Alumina

2072

α

RT

hcp (Trigonal)

[39]

 

γ

4 700

FCC ( Cubic)

θ

4 800

FCC (Monoclinic)

δ

4 1000

FCC (Tetragonal)

α

4 1100

hcp (Trigonal)

Zirconia

2700

Monoclinic

RT

Monoclinic

[40]

 

Tetragonal

4 1170

Tetragonal

Cubic

4 2370

Cubic

104

G. Perumal et al. / Wear 311 (2014) 101 113

alumina viz., intermediate metastable γ-Al 2 O 3 which is the major phase and smaller traces of α-Al 2 O 3 (Fig. 1d). Fig. 1b and e present the XRD results of 8YSZ feedstock and its corresponding coating respectively. XRD results show that both coating and powder are composed of pure metastable tetragonal zirconia which is the stable phase at higher temperature. However, discrepancy in the peak intensities among the feed stocks and coating was observed. The peak corresponding to tetragonal zirconia at 2θ ¼ 30.21 in the feed stock disappears in the coating and few new peaks appeared in the coating at different 2θ values when compared to that of the powders. The XRD pattern of both as-blended composite powders and as-sprayed composite coatings are shown in Fig. 1c and f respec- tively. The presence of high temperature stable tetragonal-ZrO 2 phase and α -Al 2 O 3 phase were observed in powders (Fig. 1c), while, the tetragonal phase of ZrO 2 along with major amount of γ-Al 2 O 3 with lower intensity of α-Al 2 O 3 is observed in the composite coating (Fig. 1f). However, the intensity of α-Al 2 O 3 in the composite coating is found to be higher than that of the alumina coating (Fig. 2d) which indicates that Al 2 O 3 powder in the alumina coating has undergone extensive melting than in the composite powders. The formation of γ-Al 2 O 3 in the alumina and alumina/zirconia composite coating is a typical phase formed in plasma sprayed alumina coatings, as this technique is associated with high temperature and rapid splat quenching. The reason for the formation of γ-Al 2 O 3 phase from α-Al 2 O 3 has been discussed by Dejang et al. [41]. Small traces of α-Al 2 O 3 in the coating are attributed to the unmelted or partially melted particles and these results are in good agreement with the earlier reports on similar types of coatings [22,23,4143]. Extensive melting and subsequent high quenching rate of splat favors the presence of high tempera- ture stable tetragonal-ZrO 2 in the 8YSZ coatings as well as in the aluminazirconia composite coating in addition to the presence of γ-Al 2 O 3 .

  • 3.2. Microstructure of the feed stock powders and coatings

Fig. 2 shows the SEM micrographs of as received micron sized Al 2 O 3 , 8YSZ, and Al 2 O 3 40 wt% 8YSZ composite blend. Al 2 O 3 powders (Fig. 2a) were of angular shape and of uniform size with mean particle size of 10 mm and 8YSZ powders (Fig. 2b) exhibit porous spherical morphology with non-uniform particles whose size ranged from 5 to 45 mm. The size and morphology of both powders conform to the details supplied by the manufacturer. After blending the micron sized Al 2 O 3 with 8YSZ powders using ball milling process as described earlier, the SEM micrograph (Fig. 2c) of composite powder shows the uniform distribution of alumina and zirconia. Figs. 3 and 4 present the SEM micrographs of surface of the as- sprayed coatings. The SEM pictures of the surface of the Al 2 O 3 coating are shown in Fig. 3a and at a higher magnication in Fig. 3b. It is found that the coating consists of smoother disk-like splats of size varying from 10 to 25 mm. SEM of the surface of the Al 2 O 3 coating also reveals very small traces of partially melted particles with uniform distribution of small pores of size ranging from 2 to 5 mm. Smoothness of splats in the Al 2 O 3 coating surface is also consistent with the surface roughness values which is given in Table 3. Formation of these smoother splats in the Al 2 O 3 coating with uniform distribution of smaller sized pores is due to exten- sive melting of in-ight particles during the spray and attening of the molten droplet upon impact on the substrate. In the case of A4Z composite coating, SEM studies revealed the presence of certain degree of partially melted particles with fully molten splats of size 1035 mm (Fig. 4a) and the presence of these splats with partially melted particles has contributed to the higher surface roughness of the composite coating compared to alumina coatings as shown in Table 3. SEM micrograph of alumina coatings taken at higher magnication clearly indicated the absence of microcracks (Fig. 4b) and presence of few unmelted particles with

100µm 100µm ZrO 2 Fig. 2. SEM morphology of as-received (a) Al 2 O 3 powders,
100µm
100µm
ZrO 2
Fig. 2. SEM morphology of as-received (a) Al 2 O 3 powders, (b) 8YSZ powders and (c) blended A4Z composite powders.
G. Perumal et al. / Wear 311 (2014) 101 –113 Fully melted splat Pores 25µm 50µm
G. Perumal et al. / Wear 311 (2014) 101 –113
Fully melted
splat
Pores
25µm
50µm

105

Fig. 3. SEM surface morphology of (a) Al 2 O 3 coating and (b) at higher
Fig. 3. SEM surface morphology of (a) Al 2 O 3 coating and (b) at higher magnification.
Fully melted
splats
Partially melted
pores
p articles
10µm
50µm

Fig. 4. SEM surface morphology of (a) Al 2 O 3 40 wt% 8YSZ coating and (b) at higher magnication.

Table 3

Roughness, porosity and microhardness of the coatings.

Coatings

Roughness (lm) Porosity (vol%) Microhardness (GPa)

Al 2 O 3

3.67

8YSZ

4.75

A4Z composite 4.52

2.42

9.43 7 3.5

3.41

5.67 7 2.1

1.34

8.86 7 1.8

very small size of uniformly distributed pores of sizes about 2 mm. This suggests that most of the particles in the composite feed stock experienced high degree of melting and spreading upon impact on the substrate. Figs. 5 and 6 show the SEM micrographs of cross section of as-sprayed Al 2 O 3 , 8YSZ and A4Z composite coatings. It was found that all the coatings are formed by layered structure and all of them exhibit dense microstructure with less porosity with pores of smaller size. Porosity values measured using image analyzer are given in Table 3 and the values obtained also agreed fairly well with the values obtained from SEM micrographs. The SEM micro- graph of the Al 2 O 3 coating (Fig. 5a) shows that only a very small amount of unmelted particles being present compared to that of 8YSZ coating (Fig. 5b) indicating that alumina particles have experienced the greatest extent of melting. SEM image of 8YSZ coating (Fig. 5b) reveals the presence of microcracks in the coat- ing/substrate interface and between the splats. It is obvious that the adhesion strength of the 8YSZ coating on TAV alloy is less and this is attributed to the high residual stress resulting from mismatch of the coefcient of thermal expansion (CTE) between tetragonal-ZrO 2 and TAV alloy whose CTE values are 12 10 6 K 1 and 8.9 10 6 K 1 respectively [44,40]. Among the three coat- ings, mismatch of coefcient of thermal expansion is the least for the case of aluminazirconia composite coating and TAV as the CTE value of the composite coat is found to be 8.5 10 6 K 1 [29]

which is very close to that of TAV which will obviously lead to minimal residual tensile stress along the coating/substrate inter- face which is the cause for the better adhesion strength of this system and absence of microcracks. The SEM pictures taken in the back scattered electron mode of A4Z composite coating is shown in Fig. 6a. It can be seen from the micrographs that the coating is composed of alternative layers of bright and dark lamella. EDX analysis (Fig. 6c and d) shows that the bright lamella corresponds to ZrO 2 with negligible amount of alumina while dark lamella corresponds to the mixture of major amount of alumina and small amount of zirconia and these features are the same as that have been reported by earlier workers [19,23,41,43]. SEM micrograph at a higher magnication of composite coating (Fig. 6b) reveals that the ZrO 2 splats in the form of at stripes (bright layer) are embedded in the alumina matrix (dark layer). The absence of microcracks between the two splats in the coating clearly demonstrated that there is a strong bonding among the splats. Composite coating also reveals uniformly distributed smal- ler pores with partially melted or unmelted particles. However, presence of partially melted particles in the composite coating is not high as compared to the ZrO 2 coatings. The presence of unmelted particles can be attributed to the melting state of feed stock which in turn is determined by the temperature distribution of the in-ight particles. It should be noted that the temperature distribution depends on the powder size, injecting velocity and plasma spray parameters [43,45].

  • 3.3. Scratch test for adhesion/cohesion strength

The results obtained from the scratch test performed on the surfaces of plasma sprayed coatings viz; onset of coating damage (critical load), type of failure and nature of cracks as well as crack length are presented in Table 4. Generally, severe aking and

106

G. Perumal et al. / Wear 311 (2014) 101 –113 Coating Unmelted/partially melted particles Pores Substrate
G. Perumal et al. / Wear 311 (2014) 101 –113
Coating
Unmelted/partially
melted particles
Pores
Substrate
50µm
50µm

Fig. 5. SEM morphology of polished cross section of (a) Al 2 O 3 coating and (b) 8YSZ coating.

106 G. Perumal et al. / Wear 311 (2014) 101 –113 Coating Unmelted/partially melted particles Pores

Fig. 6. SEM morphology of polished cross section of (a) A4Z composite coating, (b) at higher magnication, (c) and (d) EDAX at point A and B respectively.

Table 4

Results of scratch test.

Coating

Critical load (N)

Nature of the crack

Crack length (mm)

Type of coating failure

Al 2 O 3

8YSZ

A4Z composite

41.62

15.39

46.02

Tensile cracks

Tensile cracks

Tensile cracks

50.38

125.42

33.83

Cohesive Adhesive and cohesive Cohesive

delamination are often observed during the scratching of hard coatings [42]. In the present study, the scratch track of plasma sprayed Al 2 O 3 coating reveals the presence of large number of tensile cracks only on the surface of the Al 2 O 3 coating layer and underlying substrate was not exposed as the coating did not spall (Fig. 7a and b). Formation of these tensile cracks are due to the tensile frictional stress present behind the trailing edge of the stylus and these stresses are balanced by the compressive frictional stresses ahead [32]. On the other hand, scratch track of A4Z composite coating (Fig. 7e and f) exhibits many short micro cracks on the coating surface instead of long tensile cracking. The scratch test on the plasma sprayed 8YSZ coatings (Fig. 7c and d) resulted in severe spallation and delamination with the exposure of

underlying substrate. In addition, the formations of large number of long tensile cracks were also observed. Thus, the scratch track of 8YSZ coating/TAV system reveals the cohesive and adhesive failure as given in Table 4. Obviously, the TAV alloy substrate underwent severe ductile deformation during the scratch testing on 8YSZ coated Ti alloy. Presence of microcracks and large volume of partially melted particles can be attributed to the poor cohesion strength between the splats in the 8YSZ coating. Severe aking and delamination that were observed in the case of 8YSZ coating were not observed in the plasma sprayed Al 2 O 3 and A4Z composite coatings. Instead of severe aking and delamination, spallation was observed in the vicinity of the scratch track and also both the coatings show plastic deformation to some degree. Thus, the plasma sprayed Al 2 O 3 and A4Z composite coatings possess higher

G. Perumal et al. / Wear 311 (2014) 101 113

107

Tensile cracks
Tensile cracks

Fig. 7. Scratch track of the coatings of (a) OM image and (b) SEM of Al 2 O 3 , (c) and (d) OM image of 8YSZ, (e) OM image and (f) SEM of A4Z composite.

bonding strength among the splats than that of the plasma sprayed 8YSZ coating. Further, interbonding strength of the coating is also character- ized by the onset of failure (critical load) and the widths of the scratch tracks. Widths of scratch tracks of both alumina and alumina/zirconia coatings are much narrower than those for the plasma sprayed 8YSZ coatings, indicating that the plasma sprayed Al 2 O 3 and A4Z composite coatings presented better scratch and wear-resistance property and high ability for plastic deformation than the 8YSZ coating. The most important conclusion that we arrive at from the above Table 4 is that the critical load required is maximum for the A4Z composite coating which indicates max- imum cohesive strength of composite coating with the substrate compared to other two coatings. Further, according to Pan et al. [24], the anti-scratch resistance of the coating (W R ), which is a measure of wear resistance is given as

W R p

1=2

H K 2

v

IC

F 3=2

n

L

ð4Þ

where, H v , F n and L respectively refer to the hardness, normal force exerted on the substrate by the sliding ball and the sliding distance. As fracture toughness K IC is directly proportional to crack growth resistance (ξ), the above can be rewritten as

W R p

H

1=2 2a

  • v ξ

F 3=2

n

L

ð5Þ

ξ is the crack growth resistance which is equal to reciprocal of the crack length and the exponent a(a 4 0), is a property related to the coating. The crack lengths measured using SEM images for different coatings are presented in Table 4 and these values were correlated with the anti-scratch resistance using Eq. (5). This correlation leads to a very signicant conclusion viz; that the wear resistance of the composite coating is maximum as the corresponding crack length is the minimum even though its hardness value is somewhat lower.

  • 3.4. Microindentation hardness

From the Vickers microindentation hardness values of Al 2 O 3 ,

8YSZ and A4Z composite coatings (Table 3), it is clearly evident

108

G. Perumal et al. / Wear 311 (2014) 101 113

that alumina coating exhibits higher hardness (9.43 7 3.5 GPa) which was 1.65 times and 1.2 times higher than 8YSZ and A4Z composite coatings respectively. YSZ coating possesses good combination of hardness and fracture toughness [46], whereas, alumina coating possessed higher hardness. Hence, addition of YSZ in Al 2 O 3 can give the composite coatings having optimum combi- nation of hardness and fracture toughness which makes the composite coating more suitable for tribological applications [4,9,46]. The obvious decrease in the hardness of alumina compo- site coating arises due to lower hardness of YSZ which is consistent with the previous reports [43,46]. Presence of pores and distribution of partially melted or unmelted particles also seem to be responsible for the reduction in hardness of the composite coatings.

  • 3.5. Wear rate of the coatings

Amongst the three different coatings, Al 2 O 3 and A4Z composite coated specimens which were subjected to wear test for 1,00,000 cycles while for 8YSZ coating, the experiment was stopped after 30,000 cycles as the coating got completely removed. Table 5 presents the wear rate and friction coefcient of the all the coatings against alumina ball in Hank 0 s solution environment. In the present work, the coefcient of friction and wear rate of TAV alloy performed in Hank 0 s solution are found to be 0.454 and 3.75 10 4 mm 3 /Nm respectively. Qu et al. [47] who has studied the wear behavior of TAV alloy against alumina ball under dry condition obtained the coefcient of friction to be 0.49 and wear rate as 5.7 10 4 mm 3 /Nm. It can be noted that the wear rate observed with Hank 0 s solution as has been done in the present work is lesser than those that were observed in the dry condition which is obviously expected as the intermediate medium acts like a lubricant. It can also be observed from Table 5 that coefcient of friction and wear rate of all the three coatings are substantially

lesser compared to the wear of the bare substrate of the TAV alloy. Further, it is obvious from Table 5 that the wear rates calculated by both weight loss and volume loss methods show the increasing trend of wear resistance in the order of A4Z composite coating,

Al 2 O 3 coating and nally 8YSZ coating. The wear rates of both the coatings as well as the ball measured in terms of the weight loss or the volume loss show obviously the same trends. It can be seen that wear rates of the coatings determined from weight loss

method vary from

0.66 10 9 to 44 10 9 g/cm. This result

clearly suggests that the wear resistance of the plasma-sprayed A4Z composite coating on TAV alloy is superior to other coatings. Many earlier reports in this connection show that porosity directly inuences the wear resistance of the coating [48,49]. Obviously, though all the coatings posses the dense microstruc- ture, the well bonded splats and higher microhardness of the alumina and A4Z composite coatings are the benecial factors for the improvement of the wear resistance. Evidently, this feature is consistent with what has been observed and discussed in connec- tion with the studies made on scratch resistance. Further, there are reports which show that the wear resistance of plasma-sprayed ceramic coatings increases with improved hardness and toughness [5052]. In the present study, the hardness of the A4Z composite coating is slightly lower than that of the Al 2 O 3 coating, whereas, the fracture toughness of the A4Z composite coating is found to be higher from previous reports [25,29] compared with that of the Al 2 O 3 coating. This combined property of optimum hardness and fracture toughness of the composite coating are attributed to its higher wear resistance. The wear rate of counterpart (alumina ball) was also deter- mined by both methods in order to obtain cumulative wear (which refers to the wear rate of both counterpart and coating). The wear rate of counterpart against the composite coating shows lower wear resistance than the alumina coating. Cumulative wear rates of all the coatings are shown in Fig. 8. It is found that the cumulative wear of 8YSZ coating increased

Table 5

Wear rate of coating and ball.

Coating

Wear loss (g)

Wear rate (g/cm) (wt loss method)

 

Wear rate (mm 3 /N m) (vol. loss method)

Friction

Coating

Ball

Coating 10 9

Ball 10 9

Coating 10 6

Ball 10 6

co-efcient (m)

Al 2 O 3

0.0015

0.00015

5.00

0.50

12.60

1.26

0.314

8YSZ

0.0132

0.00032

44.00

1.06

25.00

9.01

0.414

A4Z

0.0002

0.00025

0.66

0.83

1.48

2.52

0.342

TAV

0.0149

0.01100

165.00

122.00

375.00

30.10

0.454

108 G. Perumal et al. / Wear 311 (2014) 101 – 113 that alumina coating exhibits

Fig. 8. Cumulative wear of (a) 8YSZ coating, (b) Al 2 O 3 coating, (c) A4Z composite coating, and (d) cumulative wear rate of different pair of coating and ball.

G. Perumal et al. / Wear 311 (2014) 101 113

109

G. Perumal et al. / Wear 311 (2014) 101 – 113 109 Fig. 9. SEM micrographs

Fig. 9. SEM micrographs of wear track of (a) Al 2 O 3 coating, (b) at higher magnication, (c) wear track of alumina ball against Al 2 O 3 coating and (d) wear track of alumina ball at higher magnications.

G. Perumal et al. / Wear 311 (2014) 101 – 113 109 Fig. 9. SEM micrographs

Fig. 10. Optical micrographs of wear track of 8YSZ coating.

linearly with number of cycles and is completely peeled off even at 30,000 cycles. In the case of alumina coating, wear rate increases upto 20,000 cycles and thereafter reaches more or less a steady state. On the other hand A4Z composite coating attains a steady state even at lesser number of cycles indicating that the cumula- tive wear is minimal among the three coatings which can be obviously seen from Fig. 8c. Fig. 8d also shows the cumulative wear rate of different pairs. Among these, the cumulative wear for the pair A4Z/alumina ball is much lower than the cumulative wear rate of the other two pairs. The above study makes us to come to a denitive conclusion that the A4Z composite coating is the best choice as it shows minimum wear rate.

  • 3.6. Wear mechanism

This section deals with the possible wear mechanisms involved in the coatings which support the observed wear data. Figs. 911

show the SEM and optical micrographs of wear track on Al 2 O 3 , 8YSZ and A4Z composite coatings and their counter parts respec- tively. SEM micrograph of worn surfaces of alumina coating is shown in Fig. 9a and b. Worn surface of alumina coating consists of grooves, microcracks, and plowing marks. It indicates that the material removal in the alumina coating is due to abrasive wear and gets enhanced by the dislodgement of grain boundaries

fracture of the surface splats. This kind of wear mechanism is

consistent with the observations made by other researchers [53,54]. Worn surfaces of 8YSZ coatings are examined by optical

microscope and are shown in Fig. 10. The worn surface of 8YSZ

coating shows that a large amount of delaminated micron sized

particles has ultimately resulted in the delamination of the coat-

ing. Fig. 11 depicts the wear track morphology of the plasma sprayed A4Z composite coating tested against alumina ball at different magnications. A network of ne cracks and chipping was observed over the zirconia rich splat. These cracks nucleated and propagated along the splat/splat boundaries and this should be the obvious reason for the delamination of composite coating. In addition to chipping and pullouts, brittle fracture was also observed in the composite coating. The same features of wear mechanism were noticed by Dejang et al. on Al 2 O 3 20 wt% ZrO 2 coating sliding against WC/Co ball [41]. Fig. 11a shows some unusual color in the wear track of composite coating unlike what is being observed in the other regions. In order to probe the above mentioned difference, EDX analysis was carried out on the worn surface and the reason for coloration is found to be due to the presence of the constituents of Hank 0 s solution (Ca, Na, and Cl) along with wear debris of alumina and zirconia. In general, in the case of thermal spray ceramic coatings the detailed study made by Hawthorne et al. [55] shows that the material removal occurs via three processes viz; (i) microchipping and plowing, (ii) debonding at splat boundaries and (iii) splat fractures in association with porosity. In the case of the coating with poor inter-splat bonding, the major material removal

110

G. Perumal et al. / Wear 311 (2014) 101 113

110 G. Perumal et al. / Wear 311 (2014) 101 – 113 Fig. 11. SEM micrographs

Fig. 11. SEM micrographs of wear track of (a) A4Z composite coating, (b) at higher magnication, (c) EDX analysis at point A, (d) wear track of alumina ball against A4Z composite coating and (e) wear track of alumina ball at higher magnications.

mechanism is debonding at splat boundaries. Typical plasma sprayed ceramic coating is built up by random stacking of impacted droplets, resulting in imperfect contact between splats and weak interbonding between splats. Hence, the cracks devel- oped preferentially at weak-bonding splat boundaries result in detachment of the coatings and an increase in wear rate [57]. When the cohesion between splats is improved, this changes the wear mechanism of debonding of splat into splat fracture and microchipping. This kind of feature has also be observed from the earlier works [54,56]. In the present work, the wear track of 8YSZ coating exhibits coating delamination and this can be attributed to the poor inter bonding of the splats. This further led to higher coefcient of friction and wear rate than the Al 2 O 3 and A4Z composite coatings. On the other hand, the wear tracks of Al 2 O 3 and A4Z composite coatings show the progressive changes in the wear mechanism of coating delamination into microcracking and microchipping. It demonstrates the higher inter-splat cohesion strengths of Al 2 O 3 and A4Z composite coating, which improves the wear resistance than 8YSZ coatings. The good cohesion strengths of Al 2 O 3 and A4Z composite coating should be due to the extensive melting and deforming of the molten

particles upon impact leading to more points of contact between splats which in turn improve the wear resistance. Further, the wear rate of A4Z composite coating is too much reduced due to the presence of tetragonal-ZrO 2 in addition to the strong bonding of splats. Tetragonal-ZrO 2 exhibits the phase transformation toughening mechanism which resists the crack propagation or deects the crack which postpones the splat delamination [41]. The wear tracks of counterface against alumina coating and A4Z composite coating are presented at different magnications in Figs. 9 and 11. The counterface wears less against the alumina coating (Fig. 9c) than against the composite coating (Fig. 11d).This result is consistent with the wear rate of alumina ball as shown in Table 5.Further, the wear mechanism of counterface against both coatings, appears to be abrasive wear (Figs. 9d and 11e) owing to high frictional force developed on the wear surface combined with the action of wear debris.

  • 3.7. Contact pressure and stress distribution in the coatings

The wear mechanism connected with all the coatings was correlated using Hertzian contact mechanics, according to which

G. Perumal et al. / Wear 311 (2014) 101 113

111

all the stresses in the contact region are directly related with the maximum contact pressure at the contact interface and it is given by the expression [63]

P 0 ¼

"

6pðE n Þ 2 π 3 R 2

# 1=3

ð7Þ

where p is the normal applied load, R is the ball radius and E n is the reduced elastic modulus for ball and disc which is calculated from

1

1 ν 1 þ 1 ν 2

E

1

E

2

2

2

E n ¼

Radius of contact circle ðaÞ ¼

3PR

4E n

1=3

Table 6

Elastic modulus of coatings poisson.

ð8Þ

ð9Þ

Coatings

Elastic modulus (GPa)

Ref

Al 2 O 3

8YSZ

A4Z composite

190 7 40

47

150 7 22

[58]

[59]

[23]

where, E 1 , E 2 are the elastic modulii of ball and disc and υ 1 , υ 2 are Poisson 0 s ratio of ball and disc respectively. For the present work, E 1 and E 2 for all the coatings were taken from the literature and are given in Table 6 and Poisson 0 s ratio is chosen as 0.25 from the work of Shackelford et al. [60]. It should be noted that density functional method has been found to be very useful in evaluating theoretically the values of Young 0 s modulus as well as Poisson 0 s ratio as has been done by Iordanova et al. [16] and one of the authors has done extensive work along this line on Ti alloys [61,62] which in principle can be

performed for these systems as well. Using the above relations, the

values of contact pressure and contact area were determined for different mating pairs and the values are given in Table 7. The values of contact pressure (P 0 ) and contact radius (a) are

used to determine the shear stress distribution along x, y and z directions for the two surfaces which are in contact using the following expressions [63] and the values of τ max is presented in Table 7.

s x ¼

s y ¼ P 0 ð1 þ υÞ

n

1

h

z

a

i

tan

1

h

a

z

io þ

1

2

1 þ

z

2

a

2

1

s z ¼ P 0

1 þ

z 2

a 2

1

ð10Þ

ð11Þ

Table 7

Reduced elastic modulus and maximum contact pressure.

Mating pairs E n (GPa) P 0 (MPa) a (mm) Max shear stress τ max (MPa)
Mating pairs
E n (GPa)
P 0 (MPa)
a (mm)
Max shear stress τ max (MPa)
Depth of max shear stress (mm)
Al 2 O 3 /Al 2 O 3 ball
8YSZ/Al 2 O 3 ball
A4Z/Al 2 O 3 ball
135.11
1611
0.0243
556.14
0.0245
44.615
775
0.0353
265.69
0.0354
114.72
1446
0.0257
498.67
0.0259

Fig. 12. Shear stress distribution in the (a) alumina coating, (b) 8YSZ coating and (c) A4Z composite coating.

112

G. Perumal et al. / Wear 311 (2014) 101 113

τ max ¼

s x s z

2

or 0:30P 0 at a depth of 0:48a ðfor υ ¼ 0:3Þ

ð12Þ

Fig. 12 shows the maximum shear stress (τ max ) and its dis-

tribution obtained using Hertzian contact theory of mating pairs.

When two surfaces are under sliding motion, the maximum shear

stress lies at a certain distance below the surface which causes

fatigue cracks initiated at the surface and being propagated to the

subsurface regions. These cracks may be connected to each other

which will lead to separation and delamination of material pieces

[64]. Cai et al. [65] have also addressed this question and found

that dominant wear occurs at the bonding interface due to shear

stress. Cracks observed in the substrate are initiated and propa-

gated mainly due to repeated shear stress subjected to the

bonding interface. From the present work, it is obvious that higher

cohesion strength with lesser contact pressure and shear stress of

the composite coating contributes for its lower wear rate than the

other coatings. The above nding which stems from the theory of

contact mechanics corroborates to the observation made by wear

track studies discussed earlier.

4. Conclusions

The experimental and theoretical studies performed on the

coatings developed on TAV alloy with Al 2 O 3 , ZrO 2 and A4Z

composite powders lead us to make the following conclusions.

Amongst the three different coatings (Al 2 O 3 , 8YSZ and A4Z),

wear resistance is found to be superior for the A4Z composite

coating. The wear resistance of A4Z composite coating is about

8 times higher than the alumina coating and more than 60 times

higher than the 8YSZ coating. Superior wear resistance of the

composite coating is attributed to its dense microstructure and

enhanced bonding strength among the splats. In addition, phase

transformation toughening mechanism due to the presence of

tetragonal-ZrO 2 in the composite coating is also a contributory

factor for its higher wear resistance. Wear track examination of the

coatings reveal that the main wear mechanism in the case of the

composite coating is due to microcracking and microchipping,

whereas, the wear mechanism of 8YSZ coating is due to the de-

bonding of splat. In the case of alumina coating one nds abrasive

wear and dislodgement of splat. SEM micrographs observed at the

cross section of all the coatings, scratch test results and calculation

based on contact mechanics is in agreement with the observed

wear mechanism and wear data. The present study clearly

demonstrates that the A4Z composite coating can be a suitable

choice for enhancing the wear behavior of TAV alloy for articial

implant applications.

Acknowledgments

One of the authors (GP) wishes to thank the chief executive

ofcer MJF.Ln. M. Saravanan and Dr. N. Anbazhaghan of V.R.S.

College of Engineering and Technology for providing their con-

tinuous support and cooperation to carry out the present work. Dr.

Geetha Manivasagam expresses her deep sense of gratitude to the

Department of Science and Technology, India for funding the

Project on Tribology of Coatings on Ti Alloys which led to the

conceptualization of the current work.

References

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