Construction of Magnesium Phosphate Chemical Conversion Coatings with Different Microstructures on Titanium to Enhance Osteogenesis and Angiogenesis.

Titanium (Ti) and its alloys are widely used as hard tissue substitutes in dentistry and orthopedics, but their low bioactivity leads to undesirable osseointegration defects in the early osteogenic phase. Surface modification is an important approach to overcome these problems. In the present study, novel magnesium phosphate (MgP) coatings with controllable structures were fabricated on the surface of Ti using the phosphate chemical conversion (PCC) method. The effects of the microstructure on the physicochemical and biological properties of the coatings on Ti were researched. The results indicated that accelerators in PCC solution were important factors affecting the microstructure and properties of the MgP coatings. In addition, the coated Ti exhibited excellent hydrophilicity, high bonding strength, and good corrosion resistance. Moreover, the biological results showed that the MgP coatings could improve the spread, proliferation, and osteogenic differentiation of mouse osteoblast cells (MC3T3-E1) and vascular differentiation of human umbilical vein endothelial cells (HUVECs), indicating that the coated Ti samples had a great effect on promoting osteogenesis and angiogenesis. Overall, this study provided a new research idea for the surface modification of conventional Ti to enhance osteogenesis and angiogenesis in different bone types for potential biomedical applications.

The Formation Process and Mechanism of the 3D Porous Network on the Sulfonated PEEK Surface.

A three-dimensional (3D) porous network can be prepared on the PEEK surface by sulfonation with enhanced osseointegration and antibacterial properties. However, few studies have been conducted on the formation mechanism of a 3D porous network. In this work, the surface and cross-sectional morphologies, chemical compositions, functional groups, surface wettability, and crystalline states of sulfonated PEEK were investigated at different sulfonation times and coagulant concentrations. The results show that the number of nodular structures and broken fibers on the sulfonated PEEK surface as well as the size of macrovoids in the cross sections increase with increasing sulfonation times when water is used as a coagulant. In contrast, dilute sulfuric acid as a coagulant can inhibit the formation of surface porous structures and macrovoids in the cross sections. Moreover, all of the sulfonated PEEK samples have the same chemical compositions but exhibit better hydrophilicity as the number of microsized pores decreases. It is proposed that non-solvent-induced phase separation (NIPS) occurs during the sulfonation process, and the formation mechanism of surface and cross-sectional morphologies is discussed. Furthermore, it is assumed that the air is trapped in the microsized pores, leaving the surface of the 3D porous network in the Cassie-wetting state. All of these preliminary results throw light on the nature of the sulfonation process and may guide further modification of the structures of sulfonated PEEK.

A Comparative Study on Microstructure, Segregation, and Mechanical Properties of Al-Si-Mg Alloy Parts Processed by GISS-HPDC and SEED-HPDC.

There are multiple routes to prepare semi-solid slurries with a globular microstructure for semi-solid forming. The variations in the microstructure of semi-solid slurries prepared using different routes may lead to significant differences in the flow behavior and mechanical properties of rheo-diecasting parts. Therefore, it is crucial to have a comprehensive understanding of the microstructure evolution associated with different slurry preparation routes and their resulting effects. In this study, the gas-induced semi-solid process (GISS) and the swirl enthalpy equilibrium device (SEED) routes were employed to prepare semi-solid Al-Si-Mg slurries for their simplicity and productivity in potential industrial applications. The prepared slurries were then injected into the shoot sleeves of a high-pressure die casting (HPDC) machine to produce tensile test bars. Subsequently, the bars underwent T6 treatment to enhance their mechanical properties. The microstructure, segregation, and mechanical properties of the samples were investigated and compared with those of conventional HPDC. The results indicated that the GISS and SEED can produce semi-solid slurries containing a spherical α-Al primary phase, as opposed to the dendritic structure commonly found in conventional castings. The liquid fraction had a significant effect on the flow behavior, resulting in variations in liquid segregation and mechanical properties. It was observed that a higher solid fraction (>75%) had a suppressing effect on surface liquid segregation. In addition, the tendency for liquid segregation gradually increased along the filling direction due to the special flow behavior of the semi-solid slurry with a low solid fraction. Furthermore, under the same die-casting process parameters, the conventional HPDC samples exhibit higher yield stress (139 ± 3 MPa) compared to SEED-HPDC and GISS-HPDC samples, which may be attributed to the small grain size and the distribution of eutectic phases. After undergoing the T6 treatment, both SEED-HPDC and GISS-HPDC samples showed a significant improvement in yield and tensile strength. These improvements are a result of solution and precipitation strengthening effects as well as the spheroidization of the eutectic Si phase. Moreover, the heat-treated SEED-HPDC samples demonstrate higher ultimate strength (336 ± 5 MPa) and elongation (13.7 ± 0.3%) in comparison to the GISS-HPDC samples (307 ± 4 MPa, 8.8 ± 0.2%) after heat treatment, mainly due to their low porosity density. These findings suggest that both GISS-HPDC and SEED-HPDC processes can be utilized to produce parts with favorable mechanical properties by implementing appropriate heat treatments. However, further investigation is required to control the porosities of GISS-HPDC samples during heat treatment.

Effect of Reaction Temperature on the Microstructure and Properties of Magnesium Phosphate Chemical Conversion Coatings on Titanium.

Magnesium phosphate (MgP) has garnered growing interest in hard tissue replacement processes due to having similar biological characteristics to calcium phosphate (CaP). In this study, an MgP coating with the newberyite (MgHPO4·3H2O) was prepared on the surface of pure titanium (Ti) using the phosphate chemical conversion (PCC) method. The influence of reaction temperature on the phase composition, microstructure, and properties of coatings was systematically researched with the use of an X-ray diffractometer (XRD), a scanning electron microscope (SEM), a laser scanning confocal microscope (LSCM), a contact angle goniometer, and a tensile testing machine. The formation mechanism of MgP coating on Ti was also explored. In addition, the corrosion resistance of the coatings on Ti was researched by assessing the electrochemical behavior in 0.9% NaCl solution using an electrochemical workstation. The results showed that temperature did not obviously affect the phase composition of the MgP coatings, but affected the growth and nucleation of newberyite crystals. In addition, an increase in reaction temperature had a great impact on properties including surface roughness, thickness, bonding strength, and corrosion resistance. Higher reaction temperatures resulted in more continuous MgP, larger grain size, higher density, and better corrosion resistance.

Calcium-Zinc Phosphate Chemical Conversion Coating Facilitates the Osteointegration of Biodegradable Zinc Alloy Implants by Orchestrating Macrophage Phenotype.

Zinc (Zn) alloys provide a new generation for orthopedic applications due to their essential physiological effects and promising degradation properties. However, excessive release of Zn ions (Zn2+ ) during degradation and the severe inflammatory microenvironment are not conducive to osseointegration, which is determined by the characteristics of the implant surface. Therefore, it is essential to modulate the release rate of Zn alloys by surface modification technology and endow them with anti-inflammatory and osteogenic effects. In this study, two kinds of phosphate chemical conversion (PCC) coatings with different compositions and morphological structures are prepared, namely Zn-P (with disk-like crystals) and Ca-Zn-P (with lamellar crystals). Although all the PCC-coated Zn implants have low cytotoxicity, Ca-Zn-P show better osteoimmunomodulation effects in several aspects: the induction of the M2-phenotype macrophage polarization and thus promotion of osteogenesis in vitro; the regulation of the bone immune microenvironment which is conducive to tissue regeneration and osseointegration in vivo; and the release of ions (through PI3K/AKT and Wnt signaling pathways) and the morphological structures (through RhoGTPase signaling pathways) act as possible mechanisms of M2 polarization. The Ca-Zn-P coating can be considered to provide new insights into bone immunomodulation and osseointegration.

Interleukin-4 assisted calcium-strontium-zinc-phosphate coating induces controllable macrophage polarization and promotes osseointegration on titanium implant.

Titanium (Ti) and its alloys are believed to be promising scaffold materials for dental and orthopedic implantation due to their ideal mechanical properties and biocompatibility. However, the host immune response always causes implant failures in the clinic. Surface modification of the Ti scaffold is an important factor in this process and has been widely studied to regulate the host immune response and to further promote bone regeneration. In this study, a calcium-strontium-zinc-phosphate (CSZP) coating was fabricated on a Ti implant surface by phosphate chemical conversion (PCC) technique, which modified the surface topography and element constituents. Here, we envisioned an accurate immunomodulation strategy via delivery of interleukin (IL)-4 to promote CSZP-mediated bone regeneration. IL-4 (0 and 40 ng/mL) was used to regulate immune response of macrophages. The mechanical properties, biocompatibility, osteogenesis, and anti-inflammatory properties were evaluated. The results showed that the CSZP coating exhibited a significant enhancement in surface roughness and hydrophilicity, but no obvious changes in proliferation or apoptosis of bone marrow mesenchymal stem cells (BMMSCs) and macrophages. In vitro, the mRNA and protein expression of osteogenic related factors in BMMSCs cultured on a CSZP coating, such as ALP and OCN, were significantly higher than those on bare Ti. In vivo, there was no enhanced bone formation but increased macrophage type 1 (M1) polarization on the CSZP coating. IL-4 could induce M2 polarization and promote osteogenesis of BMMSCs on CSZP in vivo and in vitro. In conclusion, the CSZP coating is an effective scaffold for BMMSCs osteogenesis, and IL-4 presents the additional advantage of modulating the immune response for bone regeneration on the CSZP coating in vivo.

Revealing nanoscale mineralization pathways of hydroxyapatite using in situ liquid cell transmission electron microscopy.

To treat impairments in hard tissues or overcome pathological calcification in soft tissues, a detailed understanding of mineralization pathways of calcium phosphate materials is needed. Here, we report a detailed mechanistic study of hydroxyapatite (HA) mineralization pathways in an artificial saliva solution via in situ liquid cell transmission electron microscopy (TEM). It is found that the mineralization of HA starts by forming ion-rich and ion-poor solutions in the saliva solution, followed by coexistence of the classical and nonclassical nucleation processes. For the nonclassical path, amorphous calcium phosphate (ACP) functions as the substrate for HA nucleation on the ACP surface, while the classical path features direct HA nucleation from the solution. The growth of HA crystals on the surface of ACP is accompanied by the ACP dissolution process. The discoveries reported in this work are important to understand the physiological and pathological formation of HA minerals, as well as to engineer the biomineralization process for bone healing and hard tissue repairs.

Efficacy of concentrated growth factors combined with mineralized collagen on quality of life and bone reconstruction of guided bone regeneration.

To evaluate the clinical efficacy of concentrated growth factors (CGFs) combined with mineralized collagen (MC) in guided bone regeneration (GBR). A retrospective study involving 29 patients treated with GBR technique, which was performed either CGF and MC complexes or MC alone. Implants were inserted simultaneously and cone-beam computed tomography was taken immediately, at 3 and 6 months postoperation. Questionnaires were completed by all patients so as to evaluate the main symptoms and daily activities during the first week after surgery. The outcomes of the two groups were statistically compared. All implants healed uneventfully. Patients in both groups suffered from different levels of discomfort for the reason of swelling, pain and chewing impairment on 1-2 days. Meanwhile, swelling of the Trial group was weaker than the Control group. When compared with the Control group, pain levels in Trial group were more rapidly reduced and patients took fewer analgesics from Day 3. Furthermore, the reconstitution mean value of the graft was thicker at 3 and 6 months in Trial group. CGFs complex with MC were beneficial to relieve the clinical symptoms, promote the peri-implant bone regeneration and shorten the healing time.

Novel PMMA bone cement nanocomposites containing magnesium phosphate nanosheets and hydroxyapatite nanofibers.

Lack of bioactivity and monomer toxicity are limiting factors of polymethyl methacrylate (PMMA) bone cement in orthopedic applications. Herein, we address these shortcomings by proposing two-dimensional magnesium phosphate (MgP) nanosheets and hydroxyapatite (HA) nanofibers as novel fillers in PMMA bone cement nanocomposites. Two-dimensional MgP nanosheets and one-dimensional HA nanofibers were synthesized by tuning the crystallization of the sodium-magnesium-phosphate ternary system and hydrothermal homogeneous precipitation, respectively. We show that MgP nanosheets exhibit antibacterial properties against Escherichia coli (E. coli). In addition, HA nanofibers with high level of bioactivity are the proper choice to induce cell viability in the nanocomposite. Results indicate that the combination of both fillers can act as deformation locks enhancing the compressive strength of the nanocomposites. The synthesized nanocomposite possesses excellent bioactivity, mechanical properties, and cytocompatibility potentially opening new paradigm in the design of next generation bone cement composites.

Investigation of nature of starting materials on the construction of hydroxyapatite 1D/3D morphologies.

With the increasing requirement of bone repair materials, hydroxyapatite (HA) has been paid widely attention to investigation because of its good bioactivity and osteoconductivity. The structure of HA is a vital factor to expand its application in the field of hard tissue therapy. Thus, many strategies have been utilized in fabricating one-dimensional (1D) and three-dimensional (3D) nanostructured HA. In this paper, we successful synthesize HA with 1D nanofibers and 3D nanostructured microspheres using stearic acid as a template and different phosphates as phosphorus sources under the same synthetic system. The morphology of HA changes from nanofibers with high flexibility to nanostructured microspheres with good sphericity under the synergistic effect of stearic acid and various phosphates. The HA nanofibers and microspheres are promising for applications in biomedical fields. Base on characterization results, the formation mechanisms of HA nanofibers and HA microspheres self-assembled by nanorods are proposed. Furthermore, the HA morphology transition from nanofibers to nanostructured microspheres may be attributed to the formation of polyphosphate-induced water-in-oil microemulsion system in the synthesis process. The finding may provide a new direction to control HA morphology from 1D nanofibers to 3D microspheres based on previous strategies.

Preparation of well-distributed titania nanopillar arrays on Ti6Al4V surface by induction heating for enhancing osteogenic differentiation of stem cells.

Great effort has recently been devoted to the preparation of nanoscale surfaces on titanium-based implants to achieve clinically fast osteoinduction and osseointegration, which relies on the unique characteristics of the nanostructure. In this work, we used induction heating treatment (IHT) as a rapid oxidation method to fabricate a porous nanoscale oxide layer on the Ti6Al4V surface for better medical application. Well-distributed vertical nanopillars were yielded by IHT for 20-35 s on the alloy surface. The composition of the oxides contained rutile/anatase TiO2 and a small amount of Al2O3 between the TiO2 grain boundaries (GBs). This technology resulted in a reduction and subsequent increase of surface roughness of 26-32 nm when upregulating the heating time, followed by the successive enhancement of the thickness, wettability and adhesion strength of the oxidation layer to the matrix. The surface hardness also distinctly rose to 554 HV in the IHT-35 s group compared with the 350 HV of bare Ti6Al4V. The massive small-angle GBs in the bare alloy promoted the formation of nanosized oxide crystallites. The grain refinement and deformation texture reduction further improved the mechanical properties of the matrix after IHT. Moreover, in vitro experiments on a mesenchymal stem cell (BMSC) culture derived from human bone marrow for 1-7 days indicated that the nanoscale layers did not cause cytotoxicity, and facilitated cell differentiation in osteoblasts by enhancing the gene and osteogenesis-related protein expressions after 1-3 weeks of culturing. The increase of the IHT time slightly advanced the BMSC proliferation and differentiation, especially during long-term culture. Our findings provide strong evidence that IHT oxidation technology is a novel nanosurface modification technology, which is potentially promising for further clinical development.

A bioactive coating with submicron-sized titania crystallites fabricated by induction heating of titanium after tensile deformations.

Thermal oxidation technology was widely investigated as one of effective surface modification method for improving the bioactivity and biocompatibility of titanium and its alloys. In this work, the induction heat oxidization method, a fast, efficient, economical and environmental protective technology, was applied to prepare the submicron-morphological oxide coating with variable rutile TiO2 equiaxed crystallites on the surface of pure Ti substrates after cold-drawing with 10-20% deformations. The results showed the plastic-deformed Ti cylinders recrystallized during induction heating treatment (IHT) for 10-20s which resulted in evolution of microstructures as well as slight improvement of microhardness. The surface characteristics of TiO2 crystallites in oxidation layers were determined by the microstructural evolutions of Ti substrate in terms of the nucleation and growth of TiO2 crystallites. Specially, the oxidized surface with 50-75nm roughness and more uniform and finer equiaxed oxide grains remarkablely improved the apatite deposition after bioactive evaluation in 1.5 × SBF for 7 days. This work provided a potential method to create controlled bioactive oxide coatings with submicro-/nano-scaled TiO2 crystallites on titanium substrate in terms of the role of metallographic microstructure in the formation process of titanium oxides.

In-situ preparation of scholzite conversion coatings on titanium and Ti-6Al-4V for biomedical applications.

A scholzite (CaZn2(PO4)2·2H2O) coating was prepared in situ on commercially pure titanium (cpTi) and Ti-6Al-4V (Ti64) substrates using the chemical conversion technology, and its phase composition and microstructure, as well as mechanical, chemical and biological properties were investigated to explore potential applications as a bioactive coating on bone implants. It is indicated that the coating consists mainly of monoclinic scholzite crystals with nano-thick laminar morphology. The crystals on cpTi aggregate to flower-like particles with the diameter of 5-10µm, while form a network structure homogeneously on Ti64. The scratch test shows that the interfacial bonding strength between the coatings and substrates is higher than 40N. Electrochemical measurements indicate that the corrosion behavior of the coatings is not inferior compared with that of oxide film on substrates. MG63 osteoblast-like cells show good adherence and significantly proliferation and differentiation characteristics on the scholzite coated cpTi and Ti64 (p<0.05) in in-vitro cell tests, demonstrating the cytocompatibility of Ti is significantly improved by the scholzite coating. It is suggested that the scholzite coating might be a promising option in hard tissue replacements for early osteogenesis.

Phosphate chemical conversion coatings on metallic substrates for biomedical application: a review.

Phosphate chemical conversion (PCC) technology has been investigated for improving the surface performance of metallic implants in the biomedical field over the last decade. The metallic materials, such as magnesium and its alloys, titanium, pure iron and stainless steel are widely used as orthopedic devices for immobilization of bone fractures in clinic. They were previously studied as metal substrates for PCC coating aiming to modify their biocompatibility and osteoconductivity. Zinc, calcium and zinc-calcium PCC coatings are frequently utilized considering their nature and the end-use. Although PCC coating has been confirmed to potentially improve the bio-performance of metallic implants in vitro and in vivo by many researchers, there are no unified standards or regulations to give quantitative appraisal of its quality and property. As such, an overview of several main phosphate phases together with their properties and behaviors in vitro and in vivo was conducted. The mechanism of phosphating was also briefly discussed. Critical qualities of PCC coating used for biomedical application including corrosion resistance, wettability and bonding strength were analyzed separately. Biological response including in vitro cell investigations and in vivo tissue response were discussed in terms of the cytocompatibility and bioactivity of PCC coating. Further investigations are proposed to develop appropriate performance evaluation measurements by combining conventional technologies and biomedical procedures.

Preparation and properties of plasma electrolytic oxidation coating on sandblasted pure titanium by a combination treatment.

Plasma electrolytic oxidation (PEO) is one of the most applicable methods to produce bioceramic coating on a dental implant and sandblasting is a primary technique to modify metal surface properties. This study aims to deposit bioceramic Ca- and P-containing coatings on sandblasted commercially pure titanium by PEO technique to improve its bioactive performance. The time-dependent modified surfaces are characterized in terms of their microstructure, phase, chemical composition, mechanical properties and bioactivities. The results show that the combination-treated coating exhibits better properties than the PEO-treated one, especially in bioactivities, as evidenced by the HA formation after immersion in simulated body fluid (SBF) for 5 days and the cell viability after seeding for 1 or 3 days. The enhancement of the modified surface is attributed to a combination of the mechanical sandblasting and the microplasma oxidation.

Ultrasonic enhancing amorphization during synthesis of calcium phosphate.

Amorphous calcium phosphate (ACP) has great application potential in biomaterials field due to its non-cytotoxicity, high bioactivity, good cytocompatibility, and so on. The results of this research demonstrated that ultrasonic obviously enhanced amorphization during synthesis of calcium phosphate. The ACP phase was relatively ideal when the solvent of Ca(NO3)2·4H2O was ethanol and the solvent of (NH4)2HPO4 was a mixture of water and ethanol, under ultrasonic. In-situ crystallization of ACP could be observed by HRTEM. The mechanism on the effects of ultrasonic on amorphization of the synthesized calcium phosphate was discussed. It was suggested that ultrasonic synthesis might be a facile method to prepare pure and safe ACP related biomaterials.

Factors influencing the deposition of hydroxyapatite coating onto hollow glass microspheres.

Hydroxyapatite (HA) and HA coated microcarriers for cell culture and delivery have attracted more attention recently, owing to the rapid progress in the field of tissue engineering. In this research, a dense and uniform HA coating with the thickness of about 2 µm was successfully deposited on hollow glass microspheres (HGM) by biomimetic process. The influences of SBF concentration, immersion time, solid/liquid ratio and activation of HGM on the deposition rate and coating characteristics were discussed. X-ray diffraction (XRD) and Fourier transform infrared spectrum (FTIR) analyses revealed that the deposited HA is poorly crystalline. The thickness of HA coating showed almost no increase after immersion in 1.5SBF for more than 15 days with the solid/liquid ratio of 1:150. At the same time, SBF concentration, solid/liquid ratio and activation treatment played vital roles in the formation of HA coating on HGM. This poorly crystallized HA coated HGM could have potential use as microcarrier for cell culture.

Surface nanocrystallization of hydroxyapatite coating.

Nanocharactered biomaterials, such as nanopowders, nanocrystalline compacts and nanostructured films, as well as materials with nanoscale roughness, have attracted much attention recently, due to their clear effects on cell response. Surface nanocrystallization of plasma-sprayed hydroxyapatite (HA) coating can be realized by conventional post-heat treatment. This study reveals that 20-30nm nanocrystals formed on HA coatings post-heat treated at 650 degrees C, and the increase in holding time increased the number of surface nanocrystals and intensified their aggregation. Hard aggregation occurred when HA coatings were repetitively post-heat treated. This indicates that the surface nanocrystallization is controllable. Cell experiments were carried out with rat calvarial osteoblasts. The post-heat treated HA coatings exhibit an obviously better osteoblast response than the as-sprayed coatings. Well-flattened cells attached themselves to the coating surfaces, with a good interaction between their filopodia and the nanocrystallized region. It is proposed that the surface nanocrystallization should be taken into account when the post-heat treatment process is introduced for the fabrication of HA coatings.

Effect of sintering on porosity, phase, and surface morphology of spray dried hydroxyapatite microspheres.

This article deals with the effect of sintering temperature on the physical and chemical characteristics of hydroxyapatite microspheres (HAMs) obtained by spray drying method. A set of specimens were sintered in a conventional furnace at 500-1100 degrees C. The surface morphology, phase composition, size distribution, specific surface area, and porosity were characterized by scanning electron microscope, X-ray diffractometer, laser diffraction particle size analyzer, and specific surface area analyzer, respectively. The results indicated that at 800 degrees C, hydroxyapatite crystals began to grow and were sintered together, which caused a drastic decrease in both the specific surface area and the pore volume. Great changes took place on the surfaces of HAMs during sintering. When the samples were sintered at the temperature of 500 and 600 degrees C, no obvious changes can be found on the surfaces of the samples, but at 800 degrees C, open-micropore surfaces came forth. Besides, the dispersibility of the samples decreased at high temperature (1100 degrees C) because small particles tended to aggregate together.

Plasma-sprayed hydroxyapatite+titania composite bond coat for hydroxyapatite coating on titanium substrate.

A two-layer hydroxyapatite (HA)/HA+TiO(2) bond coat composite coating (HTH coating) on titanium was fabricated by plasma spraying. The HA+TiO(2) bond coat (HTBC) consists of 50 vol% HA and 50 vol% TiO(2) (HT). The microstructural characterization of the HTH coatings before and after heat treatment was conducted by using scanning electron microscopy (SEM), electron probe microanalyser (EPMA), X-ray diffractometer (XRD) and transmission electron microscopy (TEM), in comparison with that of HT coating and pure HA coating. The results revealed that HA and TiO(2) phases layered in an alternating pattern within the HTBC, and the HTBC bonded well to HA top coating (HAT coating) and Ti substrate. The as-sprayed HT coating consists mainly of crystalline HA, rutile TiO(2) and amorphous Ca-P phase. The post-spray heat treatment at 650 degrees C for 120 min effectively restores the structural integrity of HA by transforming non-HA phases into HA. It was found that there exists interdiffusion of the elements within the HTBC, but no chemical product between HA and TiO(2), such as CaTiO(3) was formed. The cross-sectional morphologies confirmed that there is a shift towards a relatively tighter bonding from the HAT coating/HTBC interface in the as-sprayed HTH coating to the HTBC/Ti substrate interface in the heat-treated HTH coating. On quenching the coatings into water, the surface cracking indicates more apparently the positive effect of the HTBC on the decrease of residual stress in HAT coating. The in situ surface cracking also suggests that the stress on the surface of the HTH coating is stable under subjection to a repetitious heat treatment. The toughening and strengthening of HTBC is thought to be mainly due to TiO(2) as obstacles embarrassing cracking, the reduction of the near-tip stresses resulting from stress-induced microcracking and the decrease of CTE mismatch. In the HTH composite coating, the HAT coating is toughened by the decreased CTE mismatch with Ti through the addition of HTBC, which bonds well to the Ti substrate via its TiO(2) hobnobbing with the Ti oxides formed on Ti substrate.