Effects of Yttria-Stabilized Zirconia on Plasma-Sprayed Hydroxyapatite/Yttria-Stabilized Zirconia Composite Coatings

The low bonding strength between hydroxyapatite (HA) and the metal substrate interface of plasma-sprayed HA coating has been a point of potential weakness in its application as a biomedical prosthesis. In the present study, yttria-stabilized (8 wt%) zirconia (YSZ) has been used to enhance the mechanical properties of HA coatings. The effects of YSZ additions (in the range 10–50 wt%) on the phase composition, microstructure, bond strength, elastic modulus, and fracture toughness of plasma-sprayed HA/YSZ composite coatings have been studied. The results indicated that decomposition of HA during plasma spraying was reduced significantly with the addition of zirconia. The higher the zirconia content, the lower the amount of calcium oxide, tricalcium phosphate, and tetracalcium phosphate formed in the coatings. In addition, there was a trace of calcium zirconate formed when less than 30 wt% zirconia was present. A solid solution of HA mixed with YSZ formed during plasma spraying; however, the amount of unmelted particles increased as the zirconia increased. The mechanical properties of the HA/YSZ composite coatings, such as bond strength, elastic modulus, and fracture toughness, increased significantly as the contents of zirconia increased.     

Enhanced bioactivity and low temperature degradation resistance of yttria stabilized zirconia/clay composites for dental applications

Yttria stabilized zirconia (YSZ)/clay composites were produced to improve osseointegration and undesired tetragonal-to-monoclinic phase transformation (low temperature degradation, LTD) of YSZ ceramics so that long-term clinical success of YSZ implants is achieved. Various amounts (0.5,1,2, and 4 wt%) of clay was incorporated to YSZ. Predetermined amounts of clay and YSZ were mixed and pressed uniaxially at 15 MPa into compacts that were subsequently pressureless sintered at 1450 °C. Density, compressive strength, hardness and indentation crack resistance of 4 wt% clay incorporated YSZ/clay composite were 5.77 ± 0.01 g/cm³, 1188 ± 121 MPa, 1223 ± 9 HV, and 4.4 ± 0.1 MPa√m, respectively. Additionally, biological properties of YSZ/clay composites were assessed in vitro using bone cells. Incorporation of 4 wt% clay significantly enhanced bone cell proliferation, spreading, and functions. Moreover, a significant increase in the LTD resistance of YSZ was achieved upon 4 wt% clay incorporation. The findings collectively suggest that YSZ/clay composites have a potential to be used as an alternative material for dental applications.     

Fabrication of ceramic composite coatings using electrophoretic deposition,reaction bonding and low temperature sintering

We have developed a novel combination of electrophoretic deposition (EPD), reaction bonding and low temperature sintering techniques for the fabrication of yttria stablised zirconia (YSZ)/alumina composite coatings on Fecralloys. A mixture of ethanol and acetylacetone solvent was found to be an effective medium for YSZ and aluminium particle suspension. With the particle size of YSZ and aluminium being significantly reduced during ball milling. By using the EPD process, uniform green form coatings containing YSZ and aluminium particles were produced on Fecralloys. After oxidation of aluminium at 500°C and sintering at 1200°C, a dense and adherent YSZ/Al₂O₃ coating was produced. The presence of aluminium in the green form coatings not only contribute to the bonding between the coating and the metal substrate, but also compensate for the volume shrinkage of the coatings during sintering by the volume expansion arising from oxidation of aluminium to alumina.     

Continuous alumina fiber-reinforced yttria-stabilized zirconia composites with high density and toughness

Continuous alumina fiber-reinforced yttria-stabilized zirconia (YSZ) composites with a LaPO₄ fiber coating were fabricated by slurry infiltration and spark plasma sintering (SPS). The LaPO₄ coating was deposited on the reinforcement alumina fabrics by a modified sol-gel method. The YSZ slurry with good dispersion and stability was prepared by optimizing the pH value, dispersant addition and ball milling time. The fabricated composite with a high density of ∼ 92 % has a good flexural strength of 277 ± 43 MPa, and a superior fracture toughness of 15.93 ± 0.75 MPa·m^1/2 exhibiting a non-brittle failure behavior. It was found that the LaPO₄ coating reduced the residual stress near the fiber/matrix interface to 131 ± 41 MPa, which was 369 ± 63 MPa in the composite without the fiber coating. The LaPO₄ coating renders a weak interphase to improve the composite toughness by activating several toughening mechanisms including crack deflection, fiber debonding and pullout, and delamination behavior.     

The influence of pH on particle packing in YSZ coatings electrophoretically deposited from a non-aqueous suspension

Yttria stabilized zirconia (YSZ) coatings were produced from a YSZ suspension in acetylacetone (ACAC) using electrophoretic deposition (EPD) and then sintered with substrate constraint at 1200 and 1300 °C. Before EPD, the operational pH of the suspension was adjusted by addition of acetic acid or triethanolamine (TEA) base. The effect of suspension pH on the deposition of EPD coatings was studied with respect to the suspension stability, coating density and microstructure. Results showed that the zeta potential had a high positive value on both sides of the iso-electric point (IEP). This probably resulted from the adsorption of TEA, detected by Fourier transform infrared spectroscopy. Three alkalies with different molecular structures were compared and the effect of their molecule length on the interparticle repulsion was discussed. Based on this, particle interactions were estimated for different pH suspensions. The reduced particle coagulation increased the packing density of the EPD coatings from 38% at pH 7.4 to 53% at pH 8.4. Therefore, subsequent sintering of coatings was promoted. The sinterability was evaluated by micro-hardness and microstructure. After sintering at 1200 °C, coatings made in pH 8.4 suspensions obtained a hardness of 786 MPa and had fewer big pores than coatings fabricated in pH 7.4 suspensions that had a hardness of 457 MPa.     

Microstructure and mechanical properties of plasma-sprayed LaMgA111O19 thick ceramic coatings

In the research, the effect of different critical plasma spray parameters (CPSP) on the microstructure and mechanical properties of plasma-sprayed LMA coatings with thickness of 797 μm were investigated. As a result, the porosity of coatings was increased from 12.14% to 24.88% with the decrease of CPSP from 1.20 to 0.86, while bonding strength of coatings was obviously reduced from 15.98 ± 0.36 MPa to 4.87 ± 0.7 MPa. Relatively, Young's modulus and hardness of the coatings exhibited a decreasing tendency with the decrease of CPSP. When the CPSP was decreased from 1.20 to 0.97, the residual compressive stress of coating surface varied from ?162.10 ± 12.13 MPa to ?93.49 ± 3.28 MPa, and that obtained from cross-section was decreased from ?116.02 ± 5.92 MPa to ?70.68 ± 3.99 MPa. Meanwhile, the fracture toughness of coating was improved from 0.62 ± 0.05MPa?m^1/2 to 1.34 ± 0.05 MPa?m^1/2, which was higher than that of cross-section of coating. The microstructure and mechanical properties of LMA thick coatings were strongly dependent on the CPSP.     

Development of yttria-stabilized zirconia and graphene coatings obtained by suspension plasma spraying: Thermal stability and influence on mechanical properties

This study investigated the feasibility of depositing graphene nanoplatelet (GNP)-reinforced yttria-stabilized zirconia (YSZ) composite coatings. The coatings were deposited from an ethanol-based mixed YSZ and GNP suspension using suspension plasma spraying (SPS). Raman spectroscopy confirmed the presence of GNPs in the YSZ matrix, and scanning electron microscopy (SEM) analysis revealed a desired columnar microstructure with GNPs distributed predominantly in the inter-columnar spacing of the YSZ matrix. The as-deposited YSZ-GNP coatings were subjected to different isothermal treatments—400, 500, and 600 °C for 8 h—to study the thermal stability of the GNPs in the composite coatings. Raman analysis showed the retention of GNPs in specimens exposed to temperatures up to 500 °C, although the defect concentration in the graphitic structure increased with increasing temperature. Only a marginal effect on the mechanical properties (i.e., hardness and fracture toughness) was observed for the isothermally treated coatings.     

Al2O3/Si3N4 nanocomposite coating on aluminum alloy by the anodizing route: Fabrication,characterization, mechanical properties and electrochemical behavior

An Al₂O₃/Si₃N₄ nanocomposite coating was successfully fabricated on commercial aluminum alloy. Hardness measurements, polarization and electrochemical impedance spectroscopy (EIS) were employed to study the mechanical and corrosion behaviors of the coatings. Field-Emission Scanning Electron Microscopy (FE-SEM) equipped with Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) were utilized to characterize the surface morphology and phase composition of the coatings. Also, coatings abrasive wear properties were evaluated with a modified ASTM G105 standard. FE-SEM image, EDS and XRD analysis revealed the presence of Si₃N₄ in the coating. Furthermore, the results showed hardness of the coatings to increase from 380±50 HV for the anodized layer to 712±36 HV for the composite coatings that were formed in an electrolyte containing 6 gr/lit Si₃N₄ nanoparticles. Electrochemical measurements indicated that corrosion resistance of the nanocomposite coating significantly increased compared to the anodized coating. In addition, the effect of Si₃N₄ nanoparticles into the nanocomposite coatings on abrasive wear mechanism and mass loss rate of the coatings was investigated.     

Composite nanostructured hydroxyapatite/yttrium stabilized zirconia dental inserts – The processing and application as dentin substitutes

The objective of the study was to process nano-structured hydroxyapatite/yttrium-stabilized zirconia bioceramic and to investigate the possibilities of its application as dentin replacement in the form of dental inserts. The processing conditions were varied in order to optimize phase composition, microstructure, fracture toughness, hardness and shear bond strength (SBS) between the obtained composite inserts and restorative materials, following either the "total-etch" or ?self-etch“ clinical protocol. Composite nano-powder, obtained by mixing and homogenization of 80?wt% of stoichiometric hydroxyapatite (HAp) synthesized by modified precipitation method and 20?wt% of yttrium-stabilized ZrO₂ (YSZ) synthesized by plasma method, was isostatically pressed into cylinder-shaped green bodies. After dilatometric analysis, HAp/YSZ inserts were sintered in the temperature range from 1200?°C to 1300?°C. Hardness and fracture toughness of sintered inserts were ranged between 3.90?±?0.20 – 3.95?±?0.12?GPa and 1.82?±?0.04 – 1.88?±?0.03 MPam^1/2, respectively. Microstructural analysis of biphasic HAp/t-ZrO₂ inserts indicated two potential fracture mechanisms for fracture toughness increasing. Sintering temperature and different clinical protocols affected SBS between processed inserts and commercial dental restorative materials. Maximum SBS values of 10.50?±?4.94?MPa (mean±standard deviation) were reached in inserts sintered at 1300?°C, following the ?self-etch“ protocol of adhesive application. It could be concluded that resin-based composites could be strongly bonded to HAp/YSZ inserts, preferably with ?self-etch“ adhesive application. In addition, the values of fracture toughness and hardness of the obtained inserts indicated the possibility of their usage as dentin substitutes, which could be a good prerequisite for satisfactory mechanics of restored teeth.     

Mechanical properties of warm sprayed HATi bio-ceramic composite coatings

To explore a new approach for fabricating the load bearing implants with the combination of bioactivity, biocompatibility, and mechanical properties, mechanically mixed hydroxyapatite (HA) and titanium (Ti) powders containing 30, 50, and 70 wt% Ti were sprayed onto a 316L stainless steel substrate using a warm spray (WS) process. The microstructures, phase compositions, chemical structures, and mechanical properties of WS HATi composite coatings were comprehensively investigated and compared to those of WS HA coating. Experimental results indicate that the cross-sectional microstructures of WS HATi composite coatings present typical lamellar structures composed of curved stripes formed by well-deformed and oxidized Ti splats and limited deformed HA splats, and are significantly influenced by the Ti content in the original powders. Phase constitutions of the composite coatings mainly consist of HA, Ti, TiO_2, and TiO. Chemical structures of HA in the composite coatings deposited using powders with Ti content less than 30% are similar to the structures in the original powder. The microhardness, elastic modulus, and bond strength of the coatings increased from 0.32 ± 0.15 GPa to 1.41 ± 0.31 GPa, from 1.37 ± 0.28 GPa to 23.28 ± 3.45 GPa, and from 17.3 ± 2.2 MPa to 34.8 ± 3.2 MPa, respectively. The abrasive wear weight loss of the coatings on Al₂O₃ abrasive paper decreased from 2.9 mg to 1 mg, as the addition of Ti particles in original powders increased from 0 to 70%.     

Improvement in thermal shock resistance of gadolinium zirconate coating by addition of nanostructured yttria partially-stabilized zirconia

Gadolinium zirconate (Gd₂Zr₂O₇, GZ) as one of the promising thermal barrier coating materials for high-temperature application in gas turbine was toughened by nanostructured 3 mol% yttria partially-stabilized zirconia (YSZ) incorporation. The fracture toughness of the composite of 90 mol% GZ-10 mol% YSZ (GZ–YSZ) was increased by about 60% relative to the monolithic GZ. Both the GZ and GZ–YSZ composite coatings were deposited by atmospheric plasma spraying on Ni-base superalloys and then thermal-shock tested under the same conditions. The thermal-shock lifetime of GZ–YSZ composite coating was improved, which is believed to be mainly attributed to the enhancement of fracture toughness by the addition of YSZ. In addition, the failure mechanisms of the thermal-shock tested GZ–YSZ composite coatings were discussed.     

Si/SiC coated Cf/SiC composites via tape casting and reaction bonding: The effect of carbon content

In this paper, a novel surface modification method for C_f/SiC composites is proposed. Si/SiC coating on C_f/SiC composites is prepared by tape casting and reaction bonding method. The effects of carbon content on the rheological property of the slurries along with the microstructure of the sintered coatings are investigated. The best result has been obtained by infiltrating liquid silicon into a porous green tape with a carbon density of 0.84 g/cm³. In addition, the effect of sintering parameters on the phase composition of the coatings is studied. Dense Si/SiC coating with high density as well as strong bonding onto the substrate is obtained. This Si/SiC coating exhibits an excellent mechanical property with HV hardness of 16.29±0.53 GPa and fracture toughness of 3.01±0.32 MPa m^1/2. Fine surface with roughness (RMS) as low as 2.164 nm is achieved after precision grinding and polishing. This study inspires a novel and effective surface modification method for C_f/SiC composites.     

Ternary hydroxyapatite/chitosan/graphene oxide composite coating on AZ91D magnesium alloy by electrophoretic deposition

In this work, ternary HA/chitosan/graphene oxide (GO) coating was applied via electrophoretic deposition on AZ91D magnesium alloy as bone implants, successfully. Subsequently, phase composition, surface morphology, hardness, corrosion behavior, bioactivity and antibacterial of the composite coatings were studied. Hardness and Young's modulus of the composite coatings increased from 40 ± 1.5 MPa and 3.1 ± 0.42 GPa to 60 ± 3.12 MPa and 8 ± 0.53 GPa for composite coatings with 0 and 2 wt% GO, respectively. The results of the SBF solution soaking of the composites after 24 days, indicated the improvement of HA growth due to the increasing of the GO addition in composite coating. New HA grains with leaf-like morphology grew uniformly at higher amounts of GO (1 and 2 %wt) in a perfectly balanced composition. Rate of the substrate corrosion significantly decreased from 4.3 to 0.2 (mpy), when the amount of GO increased from 0 to 2 wt% due to reduction of the surface cracks at the presence of the GO reinforcement. Also, there was no Escherichia coli and Staphylococcus aureus bacteria growth in broth medium after 24 h and OD₆₀₀ results at 24 h post inoculation for the 2%wt GO addition in coating.     

Improving the surface hardness of zirconia toughened alumina (ZTA) composites by surface treatment with a boehmite sol

This paper reports a novel way of enhancing the hardness of a zirconia-toughened alumina (ZTA) composite with a zirconia content of 20 vol% by surface treatments with a boehmite sol. More specifically, a ZTA composite was first prepared by heat-treating a mixture of alumina and zirconia powders containing Cr₂O₃ and SrAl₁₁CrO₁₉, as a reinforcement at 1400 °C for 1 h, and then infiltrating them with the boehmite sol, followed by heat-treatment at 1650 °C for 1 h to densify them. This treatment led to a significant increase in the surface hardness of the ZTA composite, which was attributed mainly to an increase in the volume fraction of an alumina phase with greater hardness, whereas the flexural strength and fracture toughness decreased slightly. The Vickers hardness, flexural strength and fracture toughness were 17.1 ± 2.5 GPa, 738 ± 88 MPa and 4.2 ± 0.11 MPa m^1/2, respectively.     

Thermal cycling performance of La2Ce2O7/50 vol.% YSZ composite thermal barrier coating with CMAS corrosion

La₂Ce₂O₇ (LC) is receiving increasing attention due to its lower thermal conductivity, better phase stability and higher sintering resistance than yttria partially stabilized zirconia (YSZ). However, the low fracture toughness and the sudden drop of CTE at approximately 350?°C greatly limit its application. In this study, the LC/50?vol.% YSZ composite TBC was deposited by supersonic atmospheric plasma spraying (SAPS). Compared to YSZ or double layered LC/YSZ coating, the thermal cycling life of LC/50?vol.% YSZ coating with CMAS attack increased by 93% or 91%. The latter possessed higher fracture toughness (1.48?±?0.26?MPa?m^1/2) than LC (0.72?±?0.15?MPa?m^1/2) and better CMAS corrosion resistance than YSZ owing to the formation of Ca₂(La_xCe_1-x)₈(SiO₄)₆O_6–4x with <001> orientation perpendicular to the coating surface. The sudden CTE decrease of LC was fully suppressed in LC/50?vol.% YSZ coating due to the change of temperature dependent residual stresses induced by YSZ.     

Constrained sintering of YSZ/Al2O3 composite coatings on metal substrates produced from eletrophoretic deposition

Yttria stabilized zirconia/alumina (YSZ/Al₂O₃) composite coatings were prepared from electrophoretic deposition (EPD), followed by sintering. The constrained sintering of the coatings on metal substrates was characterized with microstructure examination using electron microscopy, mechanical properties examination using nanoindentation, and residual stress measurement using Cr³⁺ fluorescence spectroscopy. The microstructure close to the coating/substrate interface is more porous than that near the surface of the EPD coatings due to the deposition process and the constrained sintering of the coatings. The sintering of the YSZ/Al₂O₃ composite coating took up to 200 h at 1250 °C to achieve the highest density due to the constraint of the substrate. When the coating was sintered at 1000 °C after sintering at 1250 °C for less than 100 h, the compressive stress was generated due to thermal mismatch between the coating and metal substrate, leading to further densification at 1000 °C because of the ‘hot pressing’ effect. The relative densities estimated based on the residual stress measurements are close to the densities measured by the Archimedes method, which excludes an open porosity effect. The densities estimated from the hardness and the modulus measurements are lower than those from the residual stress measurement and the Archimedes method, because it takes account of the open porosity.     

Effect of Dy2O3 content on microstructure and mechanical properties of zirconia-toughened alumina

In this study, the effect of adding Dy₂O₃ on the microstructure and mechanical properties of zirconia-toughened alumina (ZTA) stabilised by yttrium oxide was investigated. ZTA-Dy₂O₃ composites with different Dy₂O₃ contents (0 wt%, 1 wt%, 2 wt%, 3 wt%, and 4 wt%) were prepared by sintering at 1600 °C for 4 h. The phases and structures of the samples were characterised through X-ray diffraction (XRD) and scanning electron microscopy (SEM). Dy₂O₃ formed a solid solution c-DYZ with YSZ, and an appropriate amount of Dy₂O₃ could refine the grains and contribute to densification. The densities, hardness, flexural strength and toughness all increased and then decreased with increasing Dy₂O₃ content, reaching maximum values of 99.2%, 1741 ± 19 HV, 449 ± 10 MPa and 5.87 ± 0.42 MPa?m^1/2, respectively, at 3 wt% Dy₂O₃ content.     

Hydroxyapatite-carboxymethyl cellulose-graphene composite coating development on AZ31 magnesium alloy: Corrosion behavior and mechanical properties

In this study, hydroxyapatite (HA) coatings containing carboxymethyl cellulose (CMC) and graphene (Gr) were developed on AZ31 magnesium alloy through two-step electrophoretic deposition method. The morphology and chemical bonding of coatings were characterized and also the phase identification was done using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction, respectively. Moreover, the corrosion behavior of the applied coatings was compared with the bare AZ31 Mg alloy substrate in the simulated body fluid by the means of potentiodynamic polarization test and electrochemical impedance spectroscopy. Obtained results revealed that the novel HA-CMC-Gr coating possesses the highest corrosion resistance compared to the HA, HA-CMC, and HA-Gr coatings due to its uniform and compact structure. To investigate the mechanical properties and to elucidate the effect of CMC on the adhesion of coating-alloy interface, pull-off test was employed, where results demonstrated that the addition of CMC increases the adhesion force from 1.06 MPa to 1.62 MPa. Besides, the modulus of elasticity and the hardness of HA and HA-Gr composite coatings were compared by applying nanoindentation test. Interestingly, it is detected that the presence of Gr has considerably increased the elastic modulus of the coating by approximately 30% in comparison to the pure HA coating.     

Evaluation of mechanical properties of YSZ TBCs doped by different ratios of Eu3+ ions after isothermal oxidation

Thermal barrier coatings (TBCs) are essential to improve the thermal insulation performance of high-temperature components. Rare earth element (Eu³⁺) doped yttrium stabilized zirconia (YSZ) TBCs have been proved to be an ideal solution for non-destructive testing of internal damages. Based on this theory, two types of coatings deposited by air plasma spray (APS) on Hastelloy-X were investigated: (1) Eu³⁺ doped YSZ (dopant ratios 1 mol%, 2 mol%, 4 mol%, respectively), (2) traditional undoped 8YSZ. Isothermal oxidation treatment at 1100 °C, in increments of 10h until the failure of the coatings are conducted to evaluate the mechanical properties of different coatings. The microscopic morphology and phase of the coatings were analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD) patterns, respectively. The indentation testing methods were used to study the apparent interfacial fracture toughness and the hardness of the ceramic top coat. Results show that the Vickers hardness of the top coat increases with the decrease of porosity in the early stage and then decreases with the heat treatment time increasing in the long-term stage. Simultaneously, compared with the undoped 8YSZ coating, the fracture toughness increased with the dopant of Eu³⁺ ions increasing, from 1 mol% to 2 mol%, nevertheless, that of 4 mol% Eu³⁺ doped YSZ decreased compared with in the undoped 8 YSZ. For all types of specimens, the interfacial fracture toughness decreases with the increase of isothermal oxidation time. Results also indicate that the content of Eu³⁺ doping does not affect the microstructure and interfacial morphology of the YSZ coating as well as the growth law of thermally grown oxides (TGO). Furthermore, EDS detection found that the Eu³⁺ ions almost do not diffuse inside the TBCs system after isothermal oxidation treatment.     

Graphene oxide/hydroxyapatite composite coatings fabricated by electrophoretic nanotechnology for biological applications

Graphene oxide (GO) was firstly employed as nanoscale reinforcement fillers in hydroxyapatite (HA) coatings by a cathodic electrophoretic deposition process, and GO/HA coatings were fabricated on pure Ti substrate. The transmission electron microscopy observation and particle size analysis of the suspensions indicated that HA nanoparticles were uniformly decorated on GO sheets, forming a large GO/HA particle group. The addition of GO into HA coatings could reduce the surface cracks and increase the coating adhesion strength from 1.55 ± 0.39 MPa (pure HA) to 2.75 ± 0.38 MPa (2 wt.% GO/HA) and 3.3 ± 0.25 MPa (5 wt.% GO/HA), respectively. Potentiodynamic polarization and electrochemical impedance spectroscopy studies indicated that the GO/HA composite coatings exhibited higher corrosion resistance in comparison with pure HA coatings in simulated body fluid. In addition, superior (around 95% cell viability for 2 wt.% GO/HA) or comparable (80–90% cell viability for 5 wt.% GO/HA) in vitro biocompatibility were observed in comparison with HA coated and uncoated Ti substrate.