In the presented work, results of adhesion measurements for different systems of steel sheet-phosphate interlayer-ceramiccoating are described. The interlayers were produced by zinc phosphating; alumina, olivine and zirconiasilica-alumina (e.g. eucor) coatings were deposited by water stabilized plasma torch WSP®. However, successful application of the WSP technique depends on the choice of correct deposition parameters preserving the hydrated phosphates from thermal destruction by the molten ceramic particles. For the adhesion measurement ISO 4624standardized test was used. Corrosion resistivity was measured by polarisation resistance and free corrosion potential in 3 % NaCl solution.
Key words

L. Mastny

P. Pokorny

V. Brozek

V. Sykora

Z. Pala

English

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411METALURGIJA 54 (2015) 2, 411-414P. POKORNY, L. MASTNY, V. SYKORA, Z. PALA, V. BROZEKBOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELS  Received – Primljeno: 2014-06-24Accepted – Prihvaćeno: 2014-10-20Preliminary Note – Prethodno priopćenjeISSN 0543-5846METABK 54(2) 411-414 (2015)UDC – UDK 547.95:666.3/7.002.4:620.193=111P. Pokorny, L. Mastny, V. Sykora, Institute of Chemical Technology Prague, Czech RepublicZ. Pala, V. Brozek, Institute of Plasma Physics ASCR v.v.i. Prague, Czech RepublicIn the presented work, results of adhesion measurements for different systems of steel sheet-phosphate interlayer-ceramic coating are described. The interlayers were produced by zinc  phosphating; alumina, olivine and zirconia-silica-alumina (e.g. eucor) coatings were deposited by water stabilized plasma torch WSP®. However, successful ap-plication of the WSP technique depends on the choice of correct deposition parameters preserving the hydrated phosphates from thermal destruction by the molten ceramic particles. For the adhesion measurement ISO 4624 standardized test was used. Corrosion resistivity was measured by polarisation resistance and free corrosion poten-tial in 3 % NaCl solution.Key words: phosphating, plasma spraying, ceramic coatings, corrosion, bond strengthINTRODUCTIONPhosphating is nowadays the highest standard of surface treatment prior to painting in automotive indus-try. The emergent layer of crystalline phosphates is due to suitable level of porosity highly apsorptive not only with respect to paint, but also to oils, waxes and lubri-cats, which can be thus reliable interlocked into the sur-face [1,2]. The adhesion improvement of paints depos-ited in environment with hight moisture is manifold when compared with unphosphated surface [3]. Phos-phating of metals is mostly performed with the aim to increase corrosion resistance [2], because it stabilizes organic pains, increases their durability and substan-tially reduces the likelihood of corrosion occurrence under the paint [4]. Phosphate layer serves also as du-rable and reliable insulation when applied on the sur-face of transformer steel sheets [5]. Nevertheless, phos-phating is most frequently used for adhesion improve-ment of various materials to ferrous substrates when the common grit blasting is not sufficient or exposition to aggressive corrosion environments is expected. This surface treatment leads to significant prolongation of working life respectless to elevated levels of moisture and in the case of coating’s failure the phosphate layer limits the progress of corrosion.    There exist several phosphate layers that are used in technical praxis according to their properties, but all of them enhance adhesion to the substrate when applied and chosen properly. Layers from Zn, Fe, Zn -Ca or Zn - Mn phosphates have not only different crystalline structure, density, hardness, cleavage, but also thermal stability and fraction of crystalline water, which plays a vital role during choice of the suitable phosphate for plasma sprayed ceramics [6]. However, phosphating does not offer much wear protection and therefore lay-ered structure can be created by e.g. deposition of thin layers or thermal coatings can be sprayed on the already phosphated surface. Combination of phosphating by CVD or PVD by magnetron sputtering is not routinely done, probably because of dimensional limits of both methods. On the other hand, plasma coatings are com-monly sprayed on comparatively large surfaces. These coating have characteristic microstructure where pres-ence of pores is no exception ranging from around 5 % in alumina or zirconia coatings to less than 1 % in the case of eucor plasma coatings. Phosphating of the sub-strate prior to plasma spraying of material whose coat-ings have higher porosity can thus lead to an important feature, i.e. corrosion protection of steel substrate that would otherwise corrode and degrade when aggressive substances penetrate through open porosity. The aim of this study is enhance the adhesion and corrosion properties of plasma sprayed ceramic coat-ings on carbon steel utilizing phosphate layers as pro-tective bondcoats. The ultimate goal is to verify the po-tential of Zn phosphate conversion coating in adhesion of the plasma sprayed ceramics while not knowing the behavior of crystal hydrates during first contact with ce-ramics particles in the molten state impinging on the phosphate surface.  Plasma sprayingPlasma spaying belongs to the group of the so called thermal spraying when usually, but not necessarily, a powder material is injected into a plasma jet. The pow-der is heated by plasma and subsequently impinges onto 412  METALURGIJA 54 (2015) 2, 411-414P. POKORNY et al.: BOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELSa substrate in a form of molten particles. Since the sub-strate is much colder, the molten droplets solidify upon impact and form the so called splats which can have morphologically complex shapes given by the nature of chemical and physical interactions. Because of rapid cooling, metastable, amorphous or generally less usual phases originate during this process. An example of characteristic morphology on the surface and in the cross-section of alumina plasma sprayed coating by wa-ter stabilized plasma gun WSP® which consists mainly of delta and gamma alumina is seen in Figures 1 and 2. The WSP® has high entalphy and can process up to 40 kg/h of corundum powder at the power of 150 kW. EXPERIMENTALThe preparation and characterization of the analysed samples was carried out following these steps: – Sheets from DX51D mild steel for cold forming with 100 × 100 × 3 mm3 dimensions were degreased and hand ground onto surface roughness Ra = 4,7 μm ± 0,7 μm. – Phosphate layed was created according to commer-cial recommendation Pragofos 1222 with NaNO2 as activator. The average area weight of Zn phosphate was 15 g/m2. – The obtained phosphate layers were analysed by X-ray diffraction (XRD) performed on X’Pert PRO MPD diffractometer with 1D detector and CuKα radiation. Energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM) were employed as well. – Thermal stability of phosphate layers was assessed by differential thermal analysis and thermogravim-etry in the range from 20 °C to 400 °C and heat rate of 10 °C/min on the air. – Taylor-Hobson Surtronic 3P analysator was used for surface roughness measurements and adhesion was analysed according to EN ISO 4624 using Loctite Hysol glue and Comtest OP1/2 apparatus. – Plasma coatings of alumina, olivine/peridot and alu-mina-zirconia-silica ceramics with commercial name Eucor were deposited by WSP.  – Corrosion resistance of the steel sheet-phosphate layer-ceramic coating was investigated by free cor-rosion potential approach. Resistance of the barrier layer, i.e. phosphates plus ceramic coating, was fur-ther analysed by measurements of polarisation re-sistance in 3 % NaCl, polarization curves were ob-tained as well and the impedance spectroscopy was employed as well. RESULTS AND DISCUSSIONMicrostruture of the two phase phosphate layer seen in Figure 3 is supplemented by XRD and DTA results in Figure 4 and Figure 5, respectively.Figure 1  Surface of plasma sprayed alumina coating, magnification 300 xFigure 2  Cross-section of alumina coating on  steel  substrate, magnification 500 xFigure  3  Structure of the two-phase phosphate layer, magnification 500 xFigure 4  Phase compositon of the phosphate layer413METALURGIJA 54 (2015) 2, 411-414P. POKORNY et al.: BOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELSDTA results show that the critical temperature is at about 160 °C when two molecules of crystalline water are lost in the surface layer of phosphate.The primary layer of the monoclinic phosphophyl-lite FeZn2(PO4)2·4H2O is very thin, nevertheless it fa-cilitates disproportional reaction, via lowering the pH of phosphating bath, when the primary layer diminishes and the presence of Zn2+ leads to the emergence of or-thorhombic hopeite Zn3(PO4)2·4H2O. Average surface roughness of the phosphated steel sheets was Ra = 1,69 μm ± 0,2 μm. When ceramics coatings are deposited onto phos-phate layers, a system or a multilayer of steel-phos-phate-WSP coating is created. The very selection of the three materials for spraying was done on purpose as (i) the eucor in the as-sprayed state is fully amorphous and its porosity is lower than 1% [7] while (ii) olivine is a ceramic with comparatively low melting point and (iii) the process of alumina spraying by WSP is the most widely used and understood. Microstructure of selected multilayer steel-phosphate-alumina coatings can be seen in Figure 6.The results of corrosion resistance analyses of the phos-phate layer - ceramic coating systems are in Figures 7 and 8. The former figure includes comparison of alu-mina coating directly on steel and with the interlayer of Zn phosphates. Low negative Ecorr value means higher corrosion resistance. Moreover, the high polarization resistance of phosphate with alumina coating in Figure 8 corresponds to much higher protection of the steel substrate against corrosion. In order to asses mechani-cal resistance and stability of the Zn phosphate layer and ceramic coatings, the alumina WSP coatings with thickness 0,3 mm ± 0,1 mm were selected and the mul-tilayers were subjected to the testing of bond strength.Figure 5  DTA and TG of the phosphate layer scraped away from the steel sheetFigure  6  Cross-section in system steel – phosphate - alumina coatingFigure 7  Free corrosion potential of the carbon steel covered by WSP alumina coating Figure 8  Polarization resistance of the carbon steel with the phosphate interlayerFigure 9  Schematic depiction of bond strength testing; from left to right: steel substrate and glue (A), steel + WSP coating + glue (B), steel + phosphate layer + glue (C), steel + phosphate layer + WSP coating + glue (D)414  METALURGIJA 54 (2015) 2, 411-414P. POKORNY et al.: BOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELSSeveral set-ups of bond strength experiments were tested, all of them are schematically depicted in Figure 9. All the experiments took place 3 days after the actual conglutination. Experiment according to the set-up B showed that there is a adhesion fracture in the coating probably caused by the penetration of the glue. However, the bond strength increased from 1 MPa to around 7 MPa when the alumina coating was combined with phos-phate layer. It should be noted that the destruction dur-ing the D set-up took place not in the alumina coating, but in the phosphate layer. The same effect was ob-served in samples with olivine and eucor coatings.CONCLUSIONSIn this work, phosphated steel sheets were sprayed by ceramic coatings which would lead to increased wear resistance while limiting the possible corrosion of the steel sheet via corrosion media penetration through open porosity of the ceramic coating. It was, indeed, found that the samples that included phosphate layer exhibited lower negative Ecorr values and higher polar-ization resistance, both of which means substantially higher corrosion protection.However, the adhesion and cohesion of the whole system is an issue. The applied phosphate layer contains components with two and four crystalline waters and the loss of two crystalline waters, or partial dehydra-tion, at around 160 °C as shown by DTA leads to the observed fact that adhesion of the phosphate layer is preserved even though molten particles of ceramic ma-terial impinged on its surface. The phosphate layer can, hence, also serve as the so called bond coat increasing adhesion of the ceramic coatings to the steel substrate.  AcknowledgmentThis project is financially supported from specific university research (MSMT No 20/2014) and Czech Science Foundation grant No. P108/12/1872.REFERENCES[1] H. Dettner, J. Elze, Handbuch der galvanotechnik Band III; Carl Hanser Verlag (ed.), München, 1969.[2] W. Rausch, Die Phosphatierung von Metallen, Eugen G. Leuze Verlag (ed.), Frankfurt am Main, 1988.[3] W. Machu, Die Phosphatierung, Verlag Chemie, Berlin, 1950.[4] E. L. Ghali, R. Potvin, Corrosion Sci. 12 (1972), 583-594.[5] P. Tegehall, R. Vannerberg, Corrosion Sci. 32 (1991) 635-652.[6] P. Pokorný, V. Brožek, L. Mastný, in METAL 2012 Confe-rence Proceedings, Brno 2012, Tanger Ltd (ed.) pp. 69-70[7] T. Chraska et al., J. Thermal Spray Technology 17 (2008) 872-877.Note:  Zdenek Pala (IPP CAS Prague, Czech Republic) is  responsible for English language

Bond strength of plasma sprayed ceramic coatings on the phosphated steels

In the presented work, results of adhesion measurements for different systems of steel sheet-phosphate interlayer-ceramiccoating are described. The interlayers were produced by zinc phosphating; alumina, olivine and zirconiasilica-alumina (e.g. eucor) coatings were deposited by water stabilized plasma torch WSP®. However, successful application of the WSP technique depends on the choice of correct deposition parameters preserving the hydrated phosphates from thermal destruction by the molten ceramic particles. For the adhesion measurement ISO 4624standardized test was used. Corrosion resistivity was measured by polarisation resistance and free corrosion potential in 3 % NaCl solution

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411 METALURGIJA 54 (2015) 2, 411-414P. POKORNY, L. MASTNY, V. SYKORA, Z. PALA, V. BROZEKBOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELS  Received – Primljeno: 2014-06-24Accepted – Prihvaćeno: 2014-10-20Preliminary Note – Prethodno priopćenjeISSN 0543-5846METABK 54(2) 411-414 (2015)UDC – UDK 547.95:666.3/7.002.4:620.193=111P. Pokorny, L. Mastny, V. Sykora, Institute of Chemical Technology Prague, Czech RepublicZ. Pala, V. Brozek, Institute of Plasma Physics ASCR v.v.i. Prague, Czech RepublicIn the presented work, results of adhesion measurements for different systems of steel sheet-phosphate interlayer-ceramic coating are described. The interlayers were produced by zinc  phosphating; alumina, olivine and zirconia-silica-alumina (e.g. eucor) coatings were deposited by water stabilized plasma torch WSP®. However, successful ap-plication of the WSP technique depends on the choice of correct deposition parameters preserving the hydrated phosphates from thermal destruction by the molten ceramic particles. For the adhesion measurement ISO 4624 standardized test was used. Corrosion resistivity was measured by polarisation resistance and free corrosion poten-tial in 3 % NaCl solution.Key words: phosphating, plasma spraying, ceramic coatings, corrosion, bond strengthINTRODUCTIONPhosphating is nowadays the highest standard of surface treatment prior to painting in automotive indus-try. The emergent layer of crystalline phosphates is due to suitable level of porosity highly apsorptive not only with respect to paint, but also to oils, waxes and lubri-cats, which can be thus reliable interlocked into the sur-face [1,2]. The adhesion improvement of paints depos-ited in environment with hight moisture is manifold when compared with unphosphated surface [3]. Phos-phating of metals is mostly performed with the aim to increase corrosion resistance [2], because it stabilizes organic pains, increases their durability and substan-tially reduces the likelihood of corrosion occurrence under the paint [4]. Phosphate layer serves also as du-rable and reliable insulation when applied on the sur-face of transformer steel sheets [5]. Nevertheless, phos-phating is most frequently used for adhesion improve-ment of various materials to ferrous substrates when the   common grit blasting is not sufficient or exposition to aggressive corrosion environments is expected. This surface treatment leads to significant prolongation of working life respectless to elevated levels of moisture and in the case of coating’s failure the phosphate layer limits the progress of corrosion.    There exist several phosphate layers that are used in technical praxis according to their properties, but all of them enhance adhesion to the substrate when applied and chosen properly. Layers from Zn, Fe, Zn -Ca or Zn - Mn phosphates have not only different crystalline structure, density, hardness, cleavage, but also thermal stability and fraction of crystalline water, which plays a vital role during choice of the suitable phosphate for plasma sprayed ceramics [6]. However, phosphating does not offer much wear protection and therefore lay-ered structure can be created by e.g. deposition of thin layers or thermal coatings can be sprayed on the already phosphated surface. Combination of phosphating by CVD or PVD by magnetron sputtering is not routinely done, probably because of dimensional limits of both methods. On the other hand, plasma coatings are com-monly sprayed on comparatively large surfaces. These coating have characteristic microstructure where pres-ence of pores is no exception ranging from around 5 % in alumina or zirconia coatings to less than 1 % in the case of eucor plasma coatings. Phosphating of the sub-strate prior to plasma spraying of material whose coat-ings have higher porosity can thus lead to an important feature, i.e. corrosion protection of steel substrate that would otherwise corrode and degrade when aggressive substances penetrate through open porosity. The aim of this study is enhance the adhesion and corrosion properties of plasma sprayed ceramic coat-ings on carbon steel utilizing phosphate layers as pro-tective bondcoats. The ultimate goal is to verify the po-tential of Zn phosphate conversion coating in adhesion of the plasma sprayed ceramics while not knowing the behavior of crystal hydrates during first contact with ce-ramics particles in the molten state impinging on the phosphate surface.  Plasma sprayingPlasma spaying belongs to the group of the so called thermal spraying when usually, but not necessarily, a powder material is injected into a plasma jet. The pow-der is heated by plasma and subsequently impinges onto 412   METALURGIJA 54 (2015) 2, 411-414P. POKORNY et al.: BOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELSa substrate in a form of molten particles. Since the sub-strate is much colder, the molten droplets solidify upon impact and form the so called splats which can have morphologically complex shapes given by the nature of chemical and physical interactions. Because of rapid cooling, metastable, amorphous or generally less usual phases originate during this process. An example of characteristic morphology on the surface and in the cross-section of alumina plasma sprayed coating by wa-ter stabilized plasma gun WSP® which consists mainly of delta and gamma alumina is seen in Figures 1 and 2. The WSP® has high entalphy and can process up to 40 kg/h of corundum powder at the power of 150 kW. EXPERIMENTALThe preparation and characterization of the analysed samples was carried out following these steps:  – Sheets from DX51D mild steel for cold forming with 100 × 100 × 3 mm3 dimensions were degreased and hand ground onto surface roughness Ra = 4,7 μm ± 0,7 μm.  – Phosphate layed was created according to commer-cial recommendation Pragofos 1222 with NaNO2 as activator. The average area weight of Zn phosphate was 15 g/m2.  – The obtained phosphate layers were analysed by X-ray diffraction (XRD) performed on X’Pert PRO MPD diffractometer with 1D detector and CuKα radiation. Energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM) were employed as well.  – Thermal stability of phosphate layers was assessed by differential thermal analysis and thermogravim-etry in the range from 20 °C to 400 °C and heat rate of 10 °C/min on the air.  – Taylor-Hobson Surtronic 3P analysator was used for surface roughness measurements and adhesion was analysed according to EN ISO 4624 using Loctite Hysol glue and Comtest OP1/2 apparatus.  – Plasma coatings of alumina, olivine/peridot and alu-mina-zirconia-silica ceramics with commercial name Eucor were deposited by WSP.   – Corrosion resistance of the steel sheet-phosphate layer-ceramic coating was investigated by free cor-rosion potential approach. Resistance of the barrier layer, i.e. phosphates plus ceramic coating, was fur-ther analysed by measurements of polarisation re-sistance in 3 % NaCl, polarization curves were ob-tained as well and the impedance spectroscopy was employed as well. RESULTS AND DISCUSSIONMicrostruture of the two phase phosphate layer seen in Figure 3 is supplemented by XRD and DTA results in Figure 4 and Figure 5, respectively.Figure 1   Surface of plasma sprayed alumina coating, magnification 300 xFigure 2   Cross-section of alumina coating on  steel  substrate, magnification 500 xFigure  3   Structure of the two-phase phosphate layer, magnification 500 xFigure 4   Phase compositon of the phosphate layer413 METALURGIJA 54 (2015) 2, 411-414P. POKORNY et al.: BOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELSDTA results show that the critical temperature is at about 160 °C when two molecules of crystalline water are lost in the surface layer of phosphate.The primary layer of the monoclinic phosphophyl-lite FeZn2(PO4)2·4H2O is very thin, nevertheless it fa-cilitates disproportional reaction, via lowering the pH of phosphating bath, when the primary layer diminishes and the presence of Zn2+ leads to the emergence of or-thorhombic hopeite Zn3(PO4)2·4H2O. Average surface roughness of the phosphated steel sheets was Ra = 1,69 μm ± 0,2 μm. When ceramics coatings are deposited onto phos-phate layers, a system or a multilayer of steel-phos-phate-WSP coating is created. The very selection of the three materials for spraying was done on purpose as (i) the eucor in the as-sprayed state is fully amorphous and its porosity is lower than 1% [7] while (ii) olivine is a ceramic with comparatively low melting point and (iii) the process of alumina spraying by WSP is the most widely used and understood. Microstructure of selected multilayer steel-phosphate-alumina coatings can be seen in Figure 6.The results of corrosion resistance analyses of the phos-phate layer - ceramic coating systems are in Figures 7 and 8. The former figure includes comparison of alu-mina coating directly on steel and with the interlayer of Zn phosphates. Low negative Ecorr value means higher corrosion resistance. Moreover, the high polarization resistance of phosphate with alumina coating in Figure 8 corresponds to much higher protection of the steel substrate against corrosion. In order to asses mechani-cal resistance and stability of the Zn phosphate layer and ceramic coatings, the alumina WSP coatings with thickness 0,3 mm ± 0,1 mm were selected and the mul-tilayers were subjected to the testing of bond strength.Figure 5   DTA and TG of the phosphate layer scraped away from the steel sheetFigure  6   Cross-section in system steel – phosphate - alumina coatingFigure 7   Free corrosion potential of the carbon steel covered by WSP alumina coating Figure 8   Polarization resistance of the carbon steel with the phosphate interlayerFigure 9   Schematic depiction of bond strength testing; from left to right: steel substrate and glue (A), steel + WSP coating + glue (B), steel + phosphate layer + glue (C), steel + phosphate layer + WSP coating + glue (D)414   METALURGIJA 54 (2015) 2, 411-414P. POKORNY et al.: BOND STRENGTH OF PLASMA SPRAYED CERAMIC COATINGS ON THE PHOSPHATED STEELSSeveral set-ups of bond strength experiments were tested, all of them are schematically depicted in Figure 9. All the experiments took place 3 days after the actual conglutination. Experiment according to the set-up B showed that there is a adhesion fracture in the coating probably caused by the penetration of the glue. However, the bond strength increased from 1 MPa to around 7 MPa when the alumina coating was combined with phos-phate layer. It should be noted that the destruction dur-ing the D set-up took place not in the alumina coating, but in the phosphate layer. The same effect was ob-served in samples with olivine and eucor coatings.CONCLUSIONSIn this work, phosphated steel sheets were sprayed by ceramic coatings which would lead to increased wear resistance while limiting the possible corrosion of the steel sheet via corrosion media penetration through open porosity of the ceramic coating. It was, indeed, found that the samples that included phosphate layer exhibited lower negative Ecorr values and higher polar-ization resistance, both of which means substantially higher corrosion protection.However, the adhesion and cohesion of the whole system is an issue. The applied phosphate layer contains components with two and four crystalline waters and the loss of two crystalline waters, or partial dehydra-tion, at around 160 °C as shown by DTA leads to the observed fact that adhesion of the phosphate layer is preserved even though molten particles of ceramic ma-terial impinged on its surface. The phosphate layer can, hence, also serve as the so called bond coat increasing adhesion of the ceramic coatings to the steel substrate.  AcknowledgmentThis project is financially supported from specific university research (MSMT No 20/2014) and Czech Science Foundation grant No. P108/12/1872.REFERENCES[1]  H. Dettner, J. Elze, Handbuch der galvanotechnik Band III; Carl Hanser Verlag (ed.), München, 1969.[2]  W. Rausch, Die Phosphatierung von Metallen, Eugen G. Leuze Verlag (ed.), Frankfurt am Main, 1988.[3]  W. Machu, Die Phosphatierung, Verlag Chemie, Berlin, 1950.[4]  E. L. Ghali, R. Potvin, Corrosion Sci. 12 (1972), 583-594.[5]  P. Tegehall, R. Vannerberg, Corrosion Sci. 32 (1991) 635-652.[6]  P. Pokorný, V. Brožek, L. Mastný, in METAL 2012 Confe-rence Proceedings, Brno 2012, Tanger Ltd (ed.) pp. 69-70[7]  T. Chraska et al., J. Thermal Spray Technology 17 (2008) 872-877.Note:   Zdenek Pala (IPP CAS Prague, Czech Republic) is  responsible for English language

Bond strength of plasma sprayed ceramic coatings on the phosphated steels

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