Improved stability of plasma-sprayed dicalcium silicate/zirconia composite coating

Dicalcium silicate/zirconia composite coatings were produced on Ti-6Al-4V substrates using atmospheric plasma spraying. Different weight ratios of zirconia (50 wt.%, 70 wt.%, 90 wt.%) were mechanically blended with dicalcium silicate (C₂S) powders as feedstocks. The composite coatings were immersed in a simulated body fluid (SBF) and a Tris-HCl solution for the in vitro appraisement of stability and long-term performance in a biological environment. The ion concentration changes of Ca, Si, and P in SBF and Tris-HCl solution were monitored using inductively-coupled plasma atomic emission spectroscopy (ICP-AES). Compared to the pure C₂S coating, our results show that the dissolution rate of the composite coatings is effectively reduced and the stability is improved by the addition of zirconia. The high content of zirconia in the coatings ensures the long-term performance in biological environment, while dissolution of C₂S in the coatings results in a higher Ca ion concentration in SBF and rapid precipitation of bone-like apatite on the composite coating surfaces indicating good bioconductivity of the coatings.     

Electrical properties of plasma-sprayed yttria-stabilized zirconia films

Yttria-stabilized zirconia films, 100 to 200 m thick, were prepared by plasma spraying. The electrical properties were investigated by complex impedance spectroscopy. The results are compared with those obtained on sintered pellets prepared with the same powders used for spraying and on commercial single crystals. The ionic conductivity and the activation energies of sprayed films and single crystals are found to be very similar, and no grain-boundary effect is observed in the film complex impedance plots. These results are explained by the high density and purity of the sprayed films.     

Hydrothermal-electrochemical codeposited hydoxyapatite/yttria-stabilized zirconia composite coating

Hydroxyapatite(HA)/yttria-stabilized zirconia(YSZ) composite coatings were deposited on titanium substrates using a hydrothermal electrochemical method in an electrolyte containing calcium, phosphate ions and YSZ particles. HA/YSZ composite coatings were prepared in different conditions with different electrolyte temperatures(100 ∼ 200°C), current densities(0.1 ∼ 10.0 mA/cm²), and particles content in bath(0 ∼ 100 g/L). The effect of YSZ additions on the phase composition, microstructure, thermal stability, corrosion behavior and the bonding strength of HA/YSZ composite coatings were studied. The results show that crystallinity of HA in HA/YSZ composite coatings increase continuously with the electrolyte temperature and close to stoichiometric HA. The n(Ca)/n(P) ratio at 200°C is about 1.67 according with stoichiometric HA. YSZ particles are imbedded uniformly between the HA crystals. The average HA crystal size are reduced owing to the additions of YSZ particles. After annealing at 1200°C, tetragonal phase YSZ tend to react with the released CaO to form cubic phase YSZ and CaZrO₃, which cause destabilization of HA to decompose into more α-TCP phase. The bonding strength between HA/YSZ composite coatings and titanium substrates increase with increasing volume content of YSZ in the composite coatings (V %). HA/YSZ composite coatings exhibit a better electrochemical behavior than pure HA coatings and uncoated Ti metals.     

甲基硅酸盐/硅酸盐复合膜的组成和性能研究

采用两步法制备甲基硅酸盐/硅酸盐复合膜,通过扫描电子显微镜(SEM)及EDS分析、红外光谱(FT-IR)分析、接触角测试、中性盐雾实验和极化曲线等对膜层的微观形貌、化学组成、疏水性及耐腐蚀性能进行了研究,并与单独的硅酸盐膜、甲基硅酸盐膜进行对比.利用电化学阻抗谱和等效电路拟合分析甲基硅酸盐/硅酸盐复合膜的防腐蚀机理.结果表明:甲基硅酸盐/硅酸盐复合膜层的外层与单独甲基硅酸钠膜的成分含量基本一致,但其微观形貌与单独甲基硅酸盐膜表面布满裂纹不同,复合膜层的表面均匀平整、没有开裂,膜层附着性好.单独硅酸盐膜为亲水性膜层,甲基硅酸盐/硅酸盐复合膜表现出疏水性,与单独硅酸盐膜相比,复合膜对腐蚀的阴极过程的抑制明显增强,极化阻抗增加至单独硅酸盐膜的5倍以上,复合膜的总阻抗值超过100 kΩ·cm2,复合膜的腐蚀电流密度比单独硅酸盐膜的降低了60％.     

Phase composition and properties of plasma-sprayed zirconia thermal barrier coatings

The use of X-ray diffraction combined with TEM analysis has been used to study the crystalline structure and change in phase composition of zirconia coatings containing 6–12 wt% Y₂O₃. The optimum composition for maximum durability, observed for coatings within this composition range, is believed to be related to the microstructure developed on rapid cooling and to the volume fractions of t′, c and m phases formed during the evolution of the coating. The amount of these phases present in commercial thermal barrier coatings has been determined using X-ray diffraction and the mechanisms of toughening deduced from TEM examination of the sections of the coatings. The results obtained are discussed in relation to the degree of toughness and hence the thermal shock resistance which is a major factor in determining service life.     

Microstructure and thermal behaviour of plasma sprayed zirconia/alumina composite coating

In thermal barrier coatings (TBC), failure occurs near or at the interface between the metallic bondcoat and topcoat. On high temperature conditions, an oxide scale which is named thermally grown oxide (TGO) occurs along the bond/topcoat interface. For diminishing the creation of TGO, a dense coating with low residual stress and thermal stress buffer layer was preferable. High hardness ceramic coatings could be obtained by gas tunnel type plasma spraying, and the deposited coating had superior property in comparison with those deposited by conventional type plasma spray method. In this study, the gas tunnel type plasma spraying system was utilized to produce a zirconia/alumina functionally graded thermal barrier coating and discussed its physical and mechanical properties, thermal behavior and high temperature oxidation resistance of the coating are discussed. Consequently, the proposed system exhibited superior mechanical properties and oxidation resistance at the expenses of a slightly lower thermal insulating effect. This interlayer is preferred in order to minimize the detrimental effect of the phase transformation of gamma-Al2O3 to alpha-Al2O3.     

Optimization of mechanical/physical properties for rubber/epoxy composite coating on asphalt concrete

Journal of Materials Science Letters -     

High temperature mechanical properties of reaction-sintered mullite/zirconia and mullite/alumina/zirconia composites

Strength and fracture toughness of reaction-sintered mullite/zirconia composites (RSMZ) and reaction-sintered mullite/alumina/zirconia composites have been investigated as a function of temperature. Thermal shock resistance has also been determined. It was found that dispersion of zirconia particles and the particular microstructure of mullite obtained by means of anin situ reaction process leads to improved properties, with a room temperature fracture toughness of about 5.25 MPa m^1/2. Up to 1000° C fracture strength and toughness values are quite high, which make these materials potential candidates for high temperature applications.     

The chemistry of dicalcium silicate mineral

Dicalcium silicate is of vital importance in several fields of silicate science. It exists in several polymorphic forms, of which one (the-form) is stable at room temperature without any stabilizer. The-form is commonly found in ordinary portland cement (OPC) in association with stabilizing ions. Stabilization of other forms,,_L,_H and_m for structural and other studies have been reported. Theoretical structural analysis using topology has been reported to be of value in understanding the stabilization process of the polymorphs. The conversion of form is at times a problem in the cement industry, in addition to the formation of unwanted compounds, such as spurrite. The-form is low in hydraulic properties but in the presence of impurities such as excess CaO over the stoichiometric ratio, shows fairly high hydraulic properties. Of the other phases, the hydraulic properties of the a forms are quite encouraging but the choice of stabilizers etc. plays a dominant role. Correlation of hydraulicity with structural properties such as crystal defects, etc., has been reported but satisfactory explanation is yet to come. The hydration products of-C₂S are quite similar to those of C₃S but the kinetics are fairly slow. In the presence of active silica, and at elevated temperatures, even the-form hydrates at a faster rate. The influence of chemical accelerators on the hydration of C₂S at room temperature is well studied and NaF is found to be one of the best accelerators. The formation of reactive-C₂S by different preparative methods shows a quite interesting trend for potential manufacture of low-temperature inorganic cement or OPC with low C₃S; even utilization of low-grade limestone could be possible. The role of C₂S in the hydration of aluminous cements is being increasingly recognized and, in fact, a newer class of cements called alumina-belite cement, etc., are being developed in which C₂S is purposely maintained as a major phase.     

Sintering behaviour and mechanical properties of hydroxyapatite and dicalcium phosphate

The sintering behaviour of powders of two calcium phosphates, namely hydroxyapatite (HA) and dicalcium phosphate (DCP), were studied at various temperatures and in various environments. The density, flexural strength and Knoop hardness of HA sintered in air for 4 h initially increased with the sintering temperature, reaching maxima at around 1150°C, and then decreased due to decomposition of HA into tri- (TCP) and tetracalcium phosphates. Sintering in vacuum caused decomposition of HA at lower temperatures, and consequently the mechanical properties were poorer than those of HA sintered in air. The densification and mechanical properties of DCP sintered in air and vacuum showed similar behaviour to those of HA. In air DCP underwent phase transformation from - to - and to -phases. In vacuum DCP started to decompose into tricalcium phosphate at 1000°C. To reduce dehydroxylation, HA powder was sintered in moisture at various temperatures up to 1350°C and X-ray diffraction study did not indicate any decomposition at the highest sintering temperature. The density, flexural strength and hardness of HA sintered in moisture increased with the sintering temperature and eventually reached plateaux at about 1300°C, but below 1200°C they were lower than those of HA sintered in air at corresponding temperatures. Thus, it is seen that dehydroxylation did not hinder sintering of HA. On the other hand, decomposition obstructed sintering of both HA and DCP.     

Electroconductive properties of zirconia/carbon nanotube aerogel composite

Electroconductive properties of zirconia/multiwalled carbon nanotube aerogel composite are investigated. The composite exhibits bulk percolation cluster-like conductivity at wide range of spatial scales. Conductive atomic force microscopy reveals the localized nature of conductive properties of the composite on the micro(nano)scopic scale and the uniformity of current distribution in all conductive areas independently of their size. The presence of unlinked conductive chains and the possibility of their linking by dissociating ions are demonstrated in experiments on registration of I–V curves during the evacuation of the composite impregnated with distilled water. The experimental data make it possible to describe the electrical properties of the composite as the properties of a circuit formed by the parallel connections of numerous voltage dividers arranged in a bulk porous structure. These features make the synthesized composite a promising candidate for use in catalysis and water vapor sensors.     

纳米TiO2/有机-无机杂化丙烯酸复合涂层机械及耐腐蚀性能的研究

在采用溶胶-凝胶法合成有机-无机杂化丙烯酸树脂的基础上,研究了纳米TiO2添加量对有机-无机杂化丙烯酸复合涂层机械和耐腐蚀等性能的影响。研究表明,当纳米TiO2添加量为15%时,涂层的性能有了较大的提高,其硬度由3H提高至6H,涂层的耐盐雾时间由100h提高到500h,涂层的阻抗值也由104Ω.cm2提高至106Ω.cm2。另外,通过扫描电镜观察了复合涂层的断面,发现涂层中纳米粒子分散均匀,并且粘接紧密,形成了较为致密的复合涂层。     

Biological responses of neonatal rat calvarial osteoblasts on plasma-sprayed HA/ZrO2 composite coating

Plasma-sprayed hydroxyapatite (HA) coating, applied to metal substrates, can induce a direct chemical bond with bone and hence achieve a biological fixation of the implant. However, the poor bonding strength between the HA coating and the substrate has been a concern for the orthopedists. In a previous study, the zirconia-reinforced hydroxyapatite composite coatings (HA/ZrO₂) could significantly improve the mechanical strength before and after soaking in simulated body fluid. This study aims to investigate the biological responses of osteoblasts on plasma-sprayed HA/ZrO₂ coating. The osteoblasts derived from neonatal rat calvarial were cultured in Dulbeccos modified Eagle medium (DMEM) with fetal bovine serum (FBS) on the surface of plasma-sprayed HA coating, HA/ZrO₂ coating, and ZrO₂ coating, respectively. The biological responses were investigated by the cell growth (1, 3, 5, and 10 days) and the cell morphology under scanning electron microscopy (SEM) (3, 6, 12, 24 and 48 h). Examination by SEM revealed that osteoblasts on HA coatings exhibit less spreading during the medium phase (6 and 12 h), while, better morphologies were observed at the latter phases (24 and 48 h). This should be derived by the dissolution of HA coating in the culture medium. On HA/ZrO₂ coating, the cells showed the poor morphologies at the latter phases (24 and 48 h). This could be explained by the no apatite formed at the surface HA/ZrO₂ coating after soaking in simulated body fluid. The lower contents of ZrO₂ coating in HA coating and the addition of other solid solution (ZrO₂–MgO, CaO–ZrO₂, ZrO₂–CeO₂) in HA coating are the two possible methods to improve the cytocompatibility of HA/ZrO₂ coating.     

Microstructural characterization of doped dicalcium silicate polymorphs

This study has shown that bothΒ- andα′-C₂S can be readily stabilized by suitable doping with BaO, B₂O₃, and P₂O₅, using a single firing at 1450° C. TheΒ-C₂S samples all have similar lamellar structures, irrespective of the dopant present, which show (100) twinning. Grain boundary phases are present in allΒ-C₂S preparations. Theα′-C₂S crystals usually contain precipitates and associated strain fields and dislocations, but a grain boundary phase was only observed inα′-C₂S stabilized by BaO. Some correlation between reactivity and presence of dislocations and strain fields has been suggested for theα′-C₂S phase.     

Laser sealing of plasma-sprayed calcia-stabilized zirconia

On leave from Scientific Research Council, Baghdad, Iraq.     

Microstructure of a plasma-sprayed superalloy coating/substrate

Five different specimen preparation techniques were employed to characterize the microstructure of a cross-section of plasma-sprayed Rene 125 coating on a Rene 125 turbine blade substrate. These methods included optical microscopy, and transmission electron microscopy on three types of replicas and on thin foils. Interface and matrix precipitates were indentified using electron diffraction and energy dispersive spectrometry, with HfO₂ and (Hf, Zr)O₂ the predominant phases at the coating/blade interface, and both (Ti, Ta)C and HfO₂ present in the coating. Those blade precipitates examined contained Hf and Ta, with some Ti and a little Co. A unique dendritic structure of was also found intermittently along the interface. The combination of the five techniques provides a wide variety of information, and is a strong tool for characterizing complex microstructures.     

聚硅氮烷/BN耐热复合涂层的制备及性能

采用聚硅氮烷作为树脂基体,h-BN作为功能粉体制备复合涂层,通过化学方法对BN进行接枝改性以改善其在复合涂层中的分散,利用FT-IR和TEM对改性前后BN的化学结构进行分析,采用SEM对复合涂层微观形貌结构进行表征,通过对不同树脂含量的复合涂层微观形貌的表征确定了复合涂层最优的树脂含量为50％(质量分数),并对复合涂层的性能进行初步测试分析.结果表明:化学改性的方法成功实现BN的表面接枝,改性后的BN在涂层中的分散性能得到了有效改善,复合涂层表现出较好的阻隔屏蔽性能和耐高温、抗氧化性能.     

Hot-pressed hydroxylapatite/monoclinic zirconia composites with improved mechanical properties

Composites of hydroxylapatite (HA) and monoclinic zirconia were hot-pressed at 1100 °C and 1200 °C under vacuum to study the phase transformations and the mechanical properties. X-ray diffraction results showed a higher phase transformation from monoclinic-ZrO₂ to tetragonal-ZrO₂ when the sintering temperature increased from 1100 °C to 1200 °C. HA decomposed faster when the amount of ZrO₂ in the composites increased. Moreover, small amount of α-TCP and CaZrO₃ was observed in the composites hot-pressed at 1200 °C. Hot-pressing at 1100 °C resulted in better mechanical properties than the hot-pressing at 1200 °C because of less reaction between HA and zirconia at 1100 °C. 40 wt% monoclinic zirconia and HA composite hot-pressed at 1100 °C resulted in promising mechanical properties which are 6.5 GPa of Vickers μ-hardness, 2.23 MPa√m of fracture toughness, and 66 MPa of diametral strength.     

铝合金基体上等离子喷涂复相陶瓷涂层力学性能研究

针对铝活塞表面容易划伤的实际,利用机械球磨法和PVA造粒技术制备复合陶瓷粉末,采用等离子喷涂法在XGFH-3铝合金表面制备复合陶瓷涂层,涂层制备过程采用氧气送粉,不喷过渡层,测试了涂层结合强度、显微硬度、耐磨性等性能。结果表明,粉末球磨96h制备的涂层结合强度最高,达到了19.07MPa,复相陶瓷涂层的显微硬度最大值达到了HV0.11105,是基体的16倍,基体单位面积磨损量远高于喷涂试样,大约为涂层磨损量的8.5倍以上,最大达到了13.6倍。