Microstructural inhomogeneity in plasma-sprayed hydroxyapatite coatings and effect of post-heat treatment

The microstructural inhomogeneity in the plasma-sprayed hydroxyapatite (HA) coatings was characterized by using electron probe microanalyser (EPMA). A simple and artful method was developed to detect the interface characteristics. All the samples for observation were ground and polished along the direction parallel to the coating surfaces. The BSE images directly and clearly showed the inhomogeneity in the as-sprayed coatings with the amorphous regions being bright gray and crystalline regions being dark gray. X-ray diffractometer (XRD) patterns indicated that after immersion in deionized water for 20 days, bone-like apatite and α-Ca₂P₂O₇ precipitated on the polished surfaces of the as-sprayed HA coatings. The post-heat treatment could eliminate the microstructural inhomogeneity in the coatings. Only β-Ca₂P₂O₇ precipitated on the surfaces of the heat-treated HA coatings. The immersed samples were re-polished till tiny substrate was bared to investigate the effect of immersion on interface. It was shown that the immersion decreased the cohesive strength of the as-sprayed coatings. There were more and broader cracks in the splats that came into contact with the substrate and amorphous phase increased toward the coating-substrate interface. Post-heat treatment was proved to reduce the peeling off of coating during re-polishing operation. It was proposed that the distributions of amorphous phase and cracks in as-sprayed coatings are detrimental to coating properties and should be modified through improving the plasma spraying processing.     

Characterization of in situ synthesized TiB2 reinforcements in iron-based composite coating

TiB₂ reinforced iron-based composite coatings can be fabricated on the mild steel substrate with a powder mixture of Ti and B₄C by plasma transferred arc (PTA) powder surfacing process. Characterizations of the TiB₂ reinforcements in the coated surface were investigated in this paper. The experimental work enables the following findings to be obtained: (i) acicular shaped and blocky formed TiB₂ phases could be synthesized in situ using PTA powder surfacing process in the iron-based composite coating. (ii) Gradient distributions of TiB₂ reinforcements appeared in the composite coating from both the vertical and horizontal direction of the coating's cross-section. Significant changes of the size, shape and volume fraction for TiB₂ particles appeared in different regions of the surface coating, due to the effects of the dilution rate and mass density. (iii) Values of coating dilution could have profound impacts on the characterization of TiB₂ reinforcements in the coated surfaces. With the increase of coating dilution, TiB₂ grain tends to be acicular shaped at the edge of the surface coating, while it remains to be granular formed in the center of the composite coating.     

Synthesis and microstructure observation of titanium carbonitride nanostructured coatings using reactive plasma spraying in atmosphere

In the present study, nanostructured titanium carbonitride (TiCN) coatings were successfully deposited by reactive plasma spraying (RPS) technology using a self-designed gas tunnel mounted on a normal plasma spray torch. The phase composition and microstructure of the TiCN coatings were characterised by XRD, SEM and TEM. The results indicated that the main phase of the coatings was FCC TiC_0.2N_0.8 with a small amount of Ti₃O. The coating that was deposited using 35 kW displayed better microstructure and properties. The coating exhibited a typical nanostructure including 90 nm diamertrical equiaxed grains and 400 nm long columnar grains by TEM images. The SEM observation further revealed that the equiaxed grains in parallel direction to the substrate surface in TEM images were actually the columnar grains perpendicular to the substrate surface. The formation mechanism of the nanostructured coatings was also discussed. The measured microhardness value of the coating was approximately 1659 Hv_100 g, and the calculated crack extension force was about 34.9 J/m².     

Diamond coating deposition by synergy of thermal and laser methods—A problem revisited

Diamond coatings were deposited by synergy of the hot filament CVD method and the pulse TEA CO₂ laser, in spectroactive and spectroinactive diamond precursor atmospheres. Resulting diamond coatings are interpreted relying on evidence of scanning electron microscopy as well as microRaman spectroscopy. Thermal synergy component (hot filament) possesses an activating agent for diamond deposition, and contributes significantly to quality and extent of diamond deposition. Laser synergy component comprises a solid surface modification as well as the spectroactive gaseous atmosphere modification. Surface modification consists in changes of the diamond coating being deposited and, at the same time, in changes of the substrate surface structure. Laser modification of the spectroactive diamond precursor atmosphere means specific consumption of the precursor, which enables to skip the deposition on a defined substrate location. The resulting process of diamond coating elimination from certain, desired locations using the CO₂ laser might contribute to tailoring diamond coatings for particular applications. Additionally, the substrate laser modification could be optimized by choice of a proper spectroactive precursor concentration, or by a laser radiation multiple pass through an absorbing medium.     

TiN对Co基合金激光熔覆层组织与性能的影响

采用5 kW CO2激光器在低碳钢表面熔覆Co基合金涂层及TiN/Co基合金复合涂层,研究了两种涂层的组织、显微硬度以及滑动磨损性能。结果表明,Co基合金涂层主要组成相为-γCo,-εCo,Cr23C6等,TiN/Co基合金复合涂层组成相为-γCo,-εCo,Cr23C6,TiN和TiC等。Co基合金涂层由发达的-γCo枝晶和其间共晶组织所组成,TiN/Co基合金涂层典型组织为等轴固溶体以及细小的共晶组织。TiN对熔覆层的组织有显著的改善作用,促使其组织细化,树枝晶向等轴晶转化,同时可显著提高Co基合金涂层的显微硬度及耐磨性能。     

Atmospheric reactive plasma sprayed Fe-Al2O3-FeAl2O4 composite coating and its property evaluation

In the present study, Fe-Al₂O₃-FeAl₂O₄ composite coatings were successfully deposited by reactive plasma sprayed Al/Fe₂O₃ agglomerated powder. Phase composition and microstructure of the coatings were determined by XRD and SEM. The results indicated that the composite coatings were principally composed of three different phases, i.e. FeAl₂O₄ phase as main framework, dispersed ball-like Fe-rich phase, and small splats of Al₂O₃ phase, and it was thought that the in situ synthesized metal phase was helpful to toughen the coating matrix. According to the results of the indentation and frictional wear tests, the composite coating exhibited excellent toughness and anti-friction properties in comparison with conventional Al₂O₃ monophase coating, though its microhardness value was a little lower than that of Al₂O₃ coating. The formation mechanism and the toughening mechanism of the composite coating were clarified in detail.     

Laser cladding of in situ TiB2/Fe composite coating on steel

To enhance the wear resistance of mechanical components, laser cladding has been applied to deposit in situ TiB₂/Fe composite coating on steel using ferrotitanium and ferroboron as the coating precursor. The phase constituents and microstructure of the composite coating were investigated using X-ray diffraction (XRD), scanning electron micrograph (SEM) and electron probe microanalysis (EPMA). Microhardness tester and block-on-ring wear tester were employed to measure the microhardness and dry-sliding wear resistance of the composite coating. Results show that defect-free composite coating with metallurgical joint to the steel substrate can be obtained. Phases presented in the coating consist of TiB₂ and α-Fe. TiB₂ particles which are formed in situ via nucleation-growth mechanism are distributed uniformly in the α-Fe matrix with blocky morphology. The microhardness and wear properties of the composite coating improved significantly in comparison to the as-received steel substrate due to the presence of the hard reinforcement TiB₂.     

Peculiarities of structural phase and elastic stress states of superhard TiN-based nanocomposite coatings

A new concept of designing nanocomposite coatings is proposed. The concept consists in microstructural self-organization through simultaneous nucleation of islands of different mutually insoluble or slightly soluble phases at the stage of coating formation. Physical principles on which to select compositions of the coatings were developed and were experimentally verified on multicomponent nanocomposite coatings. With a Sprut magnetron arc plasma complex, superhard (H _μ > 40 GPa) multicomponent nanocomposite coatings of the system Ti-Al-Si-Cr-Ni-Cu-O-C-N were obtained. The peculiarities of structural phase and elastic stress states of the multicomponent coatings before and after annealing at a temperature of up to 1000 °C were studied by transmission electron microscopy, X-ray diffraction analysis, microhardness measurements and scratch tests. The study reveals a wide range of lattice bending-torsion (up to 200° μm^?1) of nanosized (less than 30 nm) coherent scattering regions in the two-level coating structure and of individual (up to 15 nm) TiN nanocrystals. Annealing of the coatings causes the two-level grain structure to relax with the formation of TiN-based nanocrystals of size less than 30–40 nm and with a decrease in lattice bending-torsion down to 40°–50° μm^?1. Comparative analysis of acoustic emission signals and tracks of the multicomponent and TiN coatings in scratch tests points to an increase in fracture ductility in the multicomponent coatings.     

Microstructure and properties of TiB2-containing coatings prepared by arc spraying

Low cost arc spraying and cored wires were used to deposit composite coatings consisting of TiB₂ and TiB₂/Al₂O₃ hard particles in a Ni(Cr) and stainless steel 304L matrix. Four coatings were prepared namely Ni(Cr)-TiB₂, Ni(Cr)-TiB₂/Al₂O₃, 304L-TiB₂ and 304L-TiB₂/Al₂O₃. The microstructural characteristics of powders and coatings were observed by scanning electron microscopy (SEM). Phase compositions of powders were analyzed by X-ray diffraction (XRD). Although all the analyzed coatings exhibited similar lamella structure, remarkable differences not only in the morphology of hard phase and matrix but also in the size and distribution of hard phases were observed from one coating to another. Tribological behavior of the coatings was analyzed in room temperature dry sliding wear tests (block-on-ring configuration), under 75 N at low velocity (0.5 m/s). The coatings showed far high wear resistance than low carbon steel substrate under same conditions examined. Wear loss of 304L-TiB₂ and Ni(Cr)-TiB₂ coatings were lower nearly 15 times than that of steel substrate. TiB₂ hard phases in coatings bonded well with metal matrix contributed to high wear resistance.     

Comparative examination of the microstructure and high temperature oxidation performance of NiCrBSi flame sprayed and pack cementation coatings

Coatings formed from NiCrBSi powder were deposited by thermal spray and pack cementation processes on low carbon steel. The microstructure and morphology of the coatings were studied by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). Flame sprayed coatings exhibited high porosity and were mechanically bonded to the substrate while pack cementation coatings were more compact and chemically bonded to the substrate. The microhardness and the high temperature oxidation resistance of the coated samples were evaluated by a Vickers microhardness tester and by thermogravimetric measurements (TG), respectively. Pack cementation coatings showed higher hardness and were more protective to high temperature environments than the flame sprayed coatings.     

Synthesis of TiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-based ceramics by plasma spraying

Structure of ceramics obtained by the plasma spray deposition of spherical TiO₂ powders has been investigated. An electron microscopy study of the surfaces and cross sections of particles in the initial powder and of the deposited ceramic coatings was performed. X-ray diffraction and Raman scattering data proved that the coatings were mainly structured as rutile. In addition, Raman and X-ray diffraction data have revealed an amorphous phase, an anatase phase, and non-stoichiometric phases Ti₈O₁₅, Ti₁₀O₁₉, Ti₇O₁₃, etc. being present in the coatings. The observed suppression of (011) and (111) XRD peaks and an increased intensity of (110) peak are indicative of a predominant orientation of grains in the synthesized ceramics. Mechanisms of formation of the complex coating structure are discussed.     

Microstructure and dry-sliding wear resistance of PTA clad (Cr, Fe)7C3/γ-Fe ceramal composite coating

A wear resistant (Cr, Fe)₇C₃/γ-Fe ceramal composite coating was fabricated on substrate of a 0.45%C carbon steel by plasma transferred arc (PTA) cladding process using the Fe-Cr-C elemental powder blends. The microstructure, microhardness and dry-sliding wear resistance of the coating were evaluated. Results shown that the plasma transferred arc clad ceramal composite coating has a rapidly solidified microstructure consisting of blocky primary (Cr, Fe)₇C₃ and the inter-blocky (Cr, Fe)₇C₃/γ-Fe eutectics and is metallurgically bonded to the 0.45%C carbon steel substrate. The ceramal composite coating has high hardness and excellent wear resistance under dry sliding wear test condition.     

Heat treatment induced intermetallic phase transition of arc-sprayed coating prepared by the wires combination of aluminum-cathode and steel-anode

A method to prepare intermetallic composite coatings employing the cost-efficient electric arc spraying twin wires assistant with suitable heat treatment was developed. In this study, a Fe-Al composite coating was produced by spraying twin wires, i.e. a carbon steel wire as the anode and an aluminum wire as the cathode. The inter-deposited Fe-Al coating was transformed in-situ to Fe-Al intermetallic composite coating after a post annealing treatment. The effect of annealing treatment conditions on phase composition, microstructure and mechanical properties of the coating was investigated by using XRD, SEM, EDS and OM as well as microhardness tester. The results show that the desirable intermetallic phases such as Fe₂Al₅, FeAl and Fe₃Al are obtained under the annealing condition. The main oxide in the coating is FeO which can partially transform to Fe₃O₄ up to the annealing condition.     

Nanostructured two-phase nc-TiN/a-(TiB2, BN) nanocomposite thin films

Thin films of Ti-B-N with different N contents were deposited on Si(1 0 0) at room temperature by reactive unbalanced close-field dc-magnetron sputtering using three Ti targets and one TiB₂ target in an Ar-N₂ gas mixture. The effect of N content on bonding structure, microstructure, phase configuration, surface roughness and mechanical properties have been investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), cross-sectional scanning electron microscopy (SEM), plan-view and cross-sectional high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and microindentation measurements. It was found that the N content significantly affected phase segregation and microstructure. The nitrogen-free TiB_0.65 films showed an amorphous compound consisting of Ti and TiB₂ (Ti-TiB₂). After adding about 28 at.% N, Ti was preferentially bonded to N to form TiN, accompanying with formation of small amounts of TiB and BN bonds. At this stage they combined TiB₂ to form a two-phase nanocomposite with microstructures comprising of nanocrystalline (nc-) TiN phase in nitrogen-containing amorphous (a-) TiB₂ matrix. Addition of more N promoted formation of BN bonding at cost of TiB₂, which resulted in formation of nanocomposite nc-TiN/a-(TiB₂, BN) thin films. A small grain less than 8 nm in size was found at low N content, and the grain size increased with increasing N content. A low microhardness value of about 20 GPa was obtained in the amorphous Ti-TiB₂ compound, and a maximum microhardness value of about 50 GPa was achieved in nc-TiN/a-TiB₂. A decrease of microhardness took place after formation of BN (i.e. amorphous matrix composed by both TiB₂ and BN) with further increasing N content, and a hardness value of about 35 GPa was followed at high N contents. The surface roughness strongly depended on the phase configuration. The higher the mole fraction of nanocrystalline TiN phase, the rougher the surface became.     

The microstructure and specific properties of La/HAP composite powder and its coating

La/HAP composite powder, a novel bioactive material, was prepared using co-precipitation method. The La/HAP coating was obtained for the first time through the dip-coating method, starting from the sols of La/HAP and TiO₂ particles. The compositions and coating of as-produced La/HAP composite powder sintered at temperatures from 300 to 750 °C were analyzed by means of X-ray diffraction (XRD). The changes of the ion groups in as-prepared La/HAP composite powder were characterized by using Fourier transform infrared (FTIR) spectroscopy. Their surface morphologies were observed by means of scanning electron microscope (SEM). The results show that the La/HAP composite powder has higher thermostability than pure HAP powder and La can refine HAP particle and restrain the decomposition of HAP. Consequently, in coating process the heat-treatment temperature is lower (750 °C) using the synthesized La/HAP powder than that using pure HAP (900 °C). The La/HAP coating mainly contains HAP, TiP or Ti₃P₅ and TiO₂ phases as well as a little CaTiO₃ crystal, a very ideal composition to enhance bioactivity of biomaterials. These unique properties of the La/HAP composite powder are beneficial to enhance the strength and bioactivity of coating when it is used as a starting material in coating process.     

Microstructure and corrosion properties of thick WC composite coating formed by plasma cladding

The thick Ni-coated WC coatings, in a matrix of Nickel-based alloys, were prepared on AISI 1045 steel using plasma cladding equipment. A pre-placed layer of uniform mixture, with different weight fractions of Ni-coated WC powder and Nickel-based alloy powder, on the steel substrate was melted at the high temperature of the plasma jet. The coating composition, microstructure and microhardness were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometer (EDS) and microhardness testing. The experimental results show that the metallurgical bond was formed between the coating and substrate. The XRD results show that the coatings contain γ-Ni, carbides (such as M₂₃C₆ and M₇C₃) and boride (such as Fe₂B, Fe₃B phases). SEM shows that all the coatings are crack-free with lower porosity (<1%). It is found that the microhardness and the electrochemical behavior of the coatings are depended on the content of Ni-coated WC powder. The corrosion mechanism for the coatings may be due to the microgalvance corrosion between the phases in the cladding coatings.     

Defects in the in situ synthesized TiB2/Fe composite coatings during PTA process

The in situ synthesized TiB₂/Fe composite coatings were deposited by the plasma transferred-arc (PTA) powder surfacing process. The macro and micro defects in the TiB₂/Fe composite coatings were investigated in this paper. It is found that heat input plays an important role in macro defects in the coatings. Only when the energy density and total heat input are appropriate will nice forming with few macro defects be obtained. As micro defects in the coatings, slag inclusions (C, Al₂O₃) and cracks often appear together. And it is found that slag inclusions and cracks tend to appear with a low dilution rate of the coatings, and their tendency decreases as the dilution rate increases.     

TiN对Co基合金激光熔覆层组织与性能的影响

采用5 kW CO2激光器在低碳钢表面熔覆Co基合金涂层及TiN/Co基合金复合涂层,研究了两种涂层的组织、显微硬度以及滑动磨损性能。结果表明,Co基合金涂层主要组成相为γ-Co,ε-Co,Cr23C6等,TiN/Co基合金复合涂层组成相为γ-Co,ε-Co,Cr23C6,TiN和TiC等。Co基合金涂层由发达的γ-Co枝晶和其间共晶组织所组成,TiN/Co基合金涂层典型组织为等轴固溶体以及细小的共晶组织。TiN对熔覆层的组织有显著的改善作用,促使其组织细化,树枝晶向等轴晶转化,同时可显著提高Co基合金涂层的显微硬度及耐磨性能。     

Effect of α-Al2O3 on the properties of cold sprayed Al/α-Al2O3 composite coatings on AZ91D magnesium alloy

Composite coatings using pure Al powder blended with α-Al₂O₃ as feedstock were deposited on AZ91D magnesium alloy substrates by cold spray (CS). The content of α-Al₂O₃ in the feedstock was 25 wt.% and 50 wt.%, respectively. The effects of α-Al₂O₃ on the porosity, microhardness, adhesion and tensile strength of the coatings were studied. Electrochemical tests were carried out in neutral 3.5 wt.% NaCl solution to evaluate the effect of α-Al₂O₃ on the corrosion behavior of the coatings. The results showed that the composite coatings possessed lower porosity, higher adhesion strength and tensile strength than cold sprayed pure Al coating. The corrosion current densities of the composite coatings were similar to that of the pure Al coating and much higher than that of bare AZ91D magnesium alloy.     

Suspension plasma sprayed composite coating using amorphous powder feedstock

Al₂O₃-ZrO₂ composite coatings were deposited by the suspension plasma spray process using molecularly mixed amorphous powders. X-ray diffraction (XRD) analysis shows that the as-sprayed coating is composed of α-Al₂O₃ and tetragonal ZrO₂ phases with grain sizes of 26 nm and 18 nm, respectively. The as-sprayed coating has 93% density with a hardness of 9.9 GPa. Heat treatment of the as-sprayed coating reveals that the Al₂O₃ and ZrO₂ phases are homogeneously distributed in the composite coating.