Effects of plasma gas composition on bond strength of hydroxyapatite/titanium composite coatings prepared by rf-plasma spraying

The effects of plasma gas composition on the bond-strength of HA/Ti composite coatings were investigated. HA/Ti composite coatings were deposited on titanium substrates by a radio-frequency (rf) thermal plasma spraying method with input powers of 10–30 kW. The ratio of the HA and Ti powders supplied into the plasma was precisely controlled by two microfeeders so as to change the coating's composition from Ti-rich at the bottom to HA-rich at its upper layer. The bond (tensile) strength of the obtained HA/Ti composite coatings was 40–65 MPa when sprayed with plasma gas containing N₂ (i.e., Ar–N₂). On the other hand, HA/Ti composite coatings prepared with plasma gas containing O₂ (i.e., Ar–O₂) had significantly lower bond strength (under 30 MPa). XRD patterns of Ti coatings without HA showed that titanium nitride and titanium dioxide formed, respectively, on titanium deposits sprayed with Ar–N₂ and Ar–O₂ plasma. Scanning electron microscopic (SEM) observation showed an acicular texture on the Ti deposits prepared with Ar–N₂ plasma. SEM observations implied that, when sprayed with Ar–O₂ plasma, a thin TiO₂ layer formed at the interfaces between the Ti splats in the deposits.     

Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties

Epoxy composites filled with both graphene oxide (GO) and diglycidyl ether of bisphenol-A functionalized GO (DGEBA–f–GO) sheets were prepared at different filler loading levels. The correlations between surface modification, morphology, dispersion/exfoliation and interfacial interaction of sheets and the corresponding mechanical and thermal properties of the composites were systematically investigated. The surface functionalization of DGEBA layer was found to effectively improve the compatibility and dispersion of GO sheets in epoxy matrix. The tensile test indicated that the DGEBA–f–GO/epoxy composites showed higher tensile modulus and strength than either the neat epoxy or the GO/epoxy composites. For epoxy composite with 0.25 wt% DGEBA–f–GO, the tensile modulus and strength increased from 3.15 ± 0.11 to 3.56 ± 0.08 GPa (∼13%) and 52.98 ± 5.82 to 92.94 ± 5.03 MPa (∼75%), respectively, compared to the neat epoxy resin. Furthermore, enhanced quasi-static fracture toughness (K_IC) was measured in case of the surface functionalization. The GO and DGEBA–f–GO at 0.25 wt% loading produced ∼26% and ∼41% improvements in K_IC values of epoxy composites, respectively. Fracture surface analysis revealed improved interfacial interaction between DGEBA–f–GO and matrix. Moreover, increased glass transition temperature and thermal stability of the DGEBA–f–GO/epoxy composites were also observed in the dynamic mechanical properties and thermo-gravimetric analysis compared to those of the GO/epoxy composites.     

Preparation of porous carbon nanofibers derived from graphene oxide/polyacrylonitrile composites as electrochemical electrode materials

Porous carbon nanofibers (CNFs) derived from graphene oxide (GO) were prepared from the carbonization of electrospun polyacrylonitrile nanofibers with up to 15 wt.% GO at 1200 °C, followed by a low-temperature activation. The activated CNFs with reduced GOs (r-GO) revealed a specific surface area and adsorption capacity of 631 m²/g and 191.2 F/g, respectively, which are significantly higher than those of pure CNFs (16 m²/g and 3.1 F/g). It is believed that rough interfaces between r-GO and CNFs introduce oxygen pathways during activation, help to produce large amounts of all types of pores compared to pure activated CNFs.     

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.     

Tribological behaviour of RF-magnetron sputter deposited hydroxyapatite coatings in physiological solution

The aim of the paper is to explore the tribological performance of hydroxyapatite (HA) coatings deposited by radio frequency (RF) magnetron sputtering on AZ31 magnesium alloy (96% Mg, 3% Al, 0.7% Zn, 0.3% Mn) for biomedical applications. In this study, the position of the samples on a substrate holder, relative to a target erosion zone was taken into consideration in order to elucidate its impact on the coating characteristics, such as composition, morphology, surface topography and tribology. Substrate rotation and arc-movement were foreseen in the experimental set-up to increase the uniformity of thin film properties. The deposited HA thin films were revealed to exhibit an increase of the Ca/P ratio from 1.83 to 1.97, a decrease of (002) texture and thickness, as the samples were shifted towards the target erosion zone. By coatings, the roughness of Mg alloy was decreased (R_{a Mg alloy}=31.3 nm; R_{a coating}=29 nm and 21 nm). The coating placed in the centre of the substrate holder showed high hardness and Young's modulus (H =8.3±0.9 GPa; E=89±10 GPa) than the coating prepared under the target erosion zone (H =6.9±1.1 GPa; E=75±6 GPa). The coating deposited under target erosion zone exhibits superior friction behaviour in simulated body fluid environment, with the friction coefficient (μ) of 0.184, while the sample located in the centre of the substrate holder possesses the friction coefficient (0.306) comparable to the AZ31 substrate (0.307). The low wear rate was determined in the case of coating deposited under target erosion zone (4.83×10⁻⁵ mm³ N⁻¹ m⁻¹) than uncoated AZ31 substrate (0.00518 mm³ N⁻¹ m⁻¹) or than coating placed in the centre of the substrate holder (0.00294 mm³ N⁻¹ m⁻¹).     

Effect of Ti particle size on mechanical and tribological properties of TiCN coatings prepared by reactive plasma spraying

Titanium carbonitride (TiCN) coatings were successfully fabricated by reactive plasma spraying (RPS) from agglomerated Ti-graphite feedstock. The effect of Ti particle size on the microstructure and phase composition of plasma sprayed TiCN coatings was investigated. The Vickers microhardness of coatings was measured by a Microhardness Test and the corresponding Weibull distribution were also analyzed. In addition, a pin-on-disk tribometer was employed to determine the trobological properties of coatings. Results show that all the coatings consist of TiC_xN_1−x (0 ≤ x ≤1) and minor Ti₂O phases, and the amount of Ti₂O increases with the increase of Ti particle size. The Weibull distribution of Vickers microhardness of all the coatings shows apparent scattering, while the coating sprayed with Ti particle size of 28 µm exhibits a relatively even distribution. Compared with the coating sprayed with Ti particle size of 14 µm or 48 µm, the coating sprayed with Ti particle size of 28 µm exhibits improved mechanical and tribological properties, which are attributed to the high microhardness and strong bonding strength.     

Effect of particle size on the mechanical properties of reaction bonded boron carbide ceramics

In the present communication, effect of boron carbide particle size on the mechanical properties such as hardness, fracture toughness and flexural strength of reaction bonded boron carbide (RBBC) ceramics were investigated. RBBC composites were produced by the reactive infiltration of molten silicon into porous preform containing boron carbide and free carbon. Boron carbide powders with mean particle size of 18.65 μm, 33.70 μm and 63.35 μm were chosen for the RBBC composites. The experimental results show that hardness increases from 1261.70±64.74 kg/mm² to 1674.90±100.00 kg/mm² and fracture toughness drops from 5.76±0.26 MPa m^1/2 to 3.4±0.37 MPa m^1/2. However, flexural strength decreases from 403.41±5.70 MPa to 256.15±25.05 MPa with the increase in particle size. Indentation induced cracks in RBBC are mainly median type and number of cracks increase with the increase of starting particle size.     

Dependence of the microstructure and properties of TiC/Ti3SiC2 composites on extra C addition

TiC/Ti₃SiC₂ composites were synthesized with Ti/Si/C and Al (in which extra C addition ranges from 0 to 25 wt.%) as starting powders by hot-pressed sintering method at 1400 °C under 30 MPa. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to evaluate the phase composition and the fracture surface. The results reveal that with the increase of extra C addition, the content of Ti₃SiC₂ phase decreases while the content of TiC phase increases. Graphite phase is detected in the samples with extra C addition of 20 wt.% and 25 wt.%. The bending strength decreases from 554.81 MPa to 57.44 MPa due to the decrease of the densification and Ti₃SiC₂ phase content. The electrical conductivity falls from 42,474.52 s/cm to 1524.95 s/cm, resulting from lower Ti₃SiC₂ phase content and higher contact resistance.     

Fabrication and compressive strength of porous hydroxyapatite scaffolds with a functionally graded core/shell structure

A novel type of porous hydroxyapatite (HA) scaffolds with a functionally graded core/shell structure was fabricated by freeze casting HA/camphene slurries with various HA contents into fugitive molds containing a graphite template with three-dimensionally interconnected pores for the creation of a highly porous core. All the fabricated samples had functionally graded core/shell structures with 3-D periodic pore networks in a core surrounded by a relatively dense shell. The overall porosity of the sample decreased from 60 to 38 vol% with increasing HA content in the HA/camphene slurry from 20 to 36 vol% due to a decrease in porosity in both the core and shell regions. In addition, the compressive strength was improved remarkably from 12 ± 1.1 to 32 ± 3.0 MPa. The in vitro cell test using a pre-osteoblast cell line showed that the samples had good biocompatibility.     

The properties of hydroxyapatite ceramic coatings produced by plasma electrolytic oxidation

Calcium phosphate coatings produced on the surface of Ti6Al4V by plasma electrolytic oxidation (PEO) using different concentrations of hydroxyapatite (HA) in a 0.12 M Na₃PO₄ (NAP) electrolyte solution was investigated. It was found that the amount of calcium phosphate particles infiltrated into the coating layer as well as the thickness and the surface roughness of the coating increased with increasing HA concentration. The porosity of the ceramic coatings indicated an inverse relationship with the concentration of HA particles dispersed in the NAP solution. The result also demonstrates that higher scratch adhesive strength was achieved using 1.5 g/L HA solution, producing a critical load of 2099 mN, while 0 g/L HA only produced a critical load of 1247 mN. The adhesion becomes independent of thickness when the concentration of HA exceeds 1.5 g/L. The failure of the coating was characterized by large periodic hemispherical chipping, while intermittent delamination was noticed with the coating embedded with HA particles. This study demonstrate the viability of using PEO to produce a thin layer of HA ceramic coating on Ti6Al4V suitable for biomedical applications.     

Effect of graphene addition on the mechanical and electrical properties of Al2O3-SiCw ceramics

This paper presents a study on graphene-reinforced Al₂O₃-SiCw ceramic composites and the relationship between graphene oxide (GO) loading and the resulting mechanical and electrical properties. Well-dispersed ceramic-GO powders were fabricated using a colloidal processing route. Dense composites were obtained via spark plasma sintering, a technique that has the ability to reduce GO to graphene in situ during the sintering process. The mechanical properties of the sintered composites were investigated. The composite with only a small amount of graphene (0.5 vol.%) showed the highest flexural strength (904 ± 56 MPa), fracture toughness (10.6 ± 0.3 MPa·m^1/2) and hardness (22 ± 0.8 GPa) with an extremely good dispersion of graphene within the ceramic matrix. In addition to these exceptional mechanical properties, the sintered composites also showed high electrical conductivity, which allows the compacts to be machined using electrical discharge machining and thus facilitates the fabrication of ceramic components with sophisticated shapes while reducing machining costs.     

Structure of the hydroxyapatite plasma-sprayed coatings deposited on pre-heated titanium substrates

Plasma spraying is the most commonly used thermal spray method for the application of hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) coatings. In the present study, the HA coatings were plasma spraying deposited onto plates of titanium pre-heated to 20 °C, 300 °C and 550 °C. The obtained HA coatings were investigated by means of X-ray diffraction and scanning electron microscopy. It is found that the coatings, in addition to HA, contain the tetracalcium phosphate (TTCP, (Ca₄(PO₄)₂O) phase (~10%) and a small amount of CaO (<2%). Crystal structure of HA in the coatings is revealed to be distorted. The PO4 tetrahedrons are deformed (Baur distortion coefficient D1(TO) ~0.2). The distances Ca1-O1 and Ca1-O2 are changed as compared to these in stoichiometric hydroxyapatite. These distortions are considered as a result of internal stresses, which are demonstrated in the broadening of peaks on X-ray diffraction pattern of HA. Microstructure of coatings consisting of flattened splats was formed by fully molten particles. The axial base texture was developed in the coatings. Ultrastructure is columnar with a preferred orientation of c-axes of the crystals parallel to the normal of plane coating n. The heating of substrate has a marked effect on the ultrastructure of coatings: the domain size increases from 790 to 1100 Å, the strain Δ decreases from 1.6·10^-3 to 1,2·10^–3, TTCP content diminishes from 12% to 7%. These results show that the effects due to heating of the substrate may be associated with partial recovery of HA microstructure.     

Simple Förster resonance energy transfer evidence for the ultrahigh quantum dot quenching efficiency by graphene oxide compared to other carbon structures

Förster resonance energy transfer (FRET) entails the transfer of energy from a photoexcited energy donor to a close energy acceptor. In this regard, quantum dots (QDs), as donors, are quenched when they are next to an acceptor material. Graphite, carbon nanotubes (CNTs), carbon nanofibers (CNFs) and graphene oxide (GO) were explored as energy acceptors of QD FRET donors in the solid phase. In our setup, the higher estimated values of quenching efficiency for each material are as follows: graphite, 66 ± 17%; CNTs, 71 ± 1%; CNFs, 74 ± 07% and GO, 97 ± 1%. Among these materials, GO is the best acceptor of QD FRET donors in the solid phase. Such an ultrahigh quenching efficiency by GO and the proposed simple mechanism may open the way to several interesting applications in the field of biosensing.     

In situ doping of diamond coatings with silicon,aluminum and titanium through a modified laser-based CVD process

The aim of this study was to demonstrate the feasibility of in situ doping of chemical vapor deposition (CVD) fabricated diamond coatings through simultaneous evaporation of solids in a CVD plasma-based process. In order to achieve maximum flexibility and energy density, a laser-based plasma-jet CVD process was chosen, and expanded with the introduction of dopant rods. The rods, with diameters varying from 0.5 mm to 3.0 mm, were fed at rates from 0.25 mm/min to > 100 mm/min, and positioned 3 mm below the optical breakthrough which generates the plasma. Gas flows of 20.0 slm (standard liters per min) argon, 2.0 slm hydrogen and 0.02 slm methane were used for diamond coating deposition. At a surface temperature of about 1100 °C, an average linear diamond growth rate of 20 μm/h was achieved. The materials selected as solid precursors for the rods were SiO₂, Al₂O₃, and Ti due to their differing electrical characteristics, as they are an insulator, semiconductor, and conductor, respectively. The evaporation rate of these rods varied by more than six orders of magnitude, from < 1 × 10^− 8 g/min (Ti) to > 7 × 10^− 2 g/min (SiO₂). The doped diamond coatings were produced by simultaneous evaporation and CVD. To prove that the precursors were vaporized and the atomic bonds were broken by the plasma, the optical emission spectra are compared with published and calculated spectral lines. Analyses of the layers were performed using EDX (energy-dispersive X-ray) spectroscopy and WDS (wavelength dispersive X-ray spectroscopy). As a result, the maximum doping densities in the diamond coating were determined, and were 3.460 wt.% for silicon, 0.957 wt.% for aluminum, and 0.03 wt.% for titanium. To prove the diamond-like characteristics of these coatings, Raman measurements were performed.     

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.     

Microstructure evolution and wear resistance of nitride/aluminide coatings on the surface of Ti-coated 2024 Al alloy during plasma nitriding

A duplex surface treatment consisting in depositing a Ti film followed by plasma nitriding was adopted to improve the wear resistance of 2024 Al alloys. Nano-grained Ti films were firstly deposited on the substrate surface by using magnetron sputtering, then plasma nitrided for 8 h at 400 °C, 430 °C, 460 °C and 490 °C, in a gas mixture of 40% N₂+60% H₂. Duplex coatings composed of three sublayers (i.e. the outmost TiN_0.3 layer, the intermediate Al₃Ti layer and the inside Al₁₈Ti₂Mg₃ layer) were obtained at nitriding temperature higher than 460 °C. The coatings obtained at 400 °C and 430 °C consisted of mainly α-TiN_0.3 with (002) preferred orientation. The surface hardness of the coatings increased at higher nitriding temperature, reaching the maximum of 500 HV at 490 °C, which was about 8 times higher than that of the uncoated alloy. The friction coefficients of 2024 Al alloy decreased in the coatings prepared at higher nitriding temperature, reaching the lowest values of 0.31 at 490 °C. The wear rate of the coated samples decreased by 56% compared with the uncoated ones. The analysis of worn surface indicated that the nitrided samples exhibited severe adhesive wear at 400 °C that changed to predominant abrasive wear at increased nitriding temperature.     

Reactive sintering cBN-Ti-Al composites by spark plasma sintering

When synthesizing polycrystalline cubic boron nitride (PcBN) at normal pressure, cBN had a trend of hexagonal transformation, which reduces the hardness and strength of PcBN. The cBN-Ti-Al composite was prepared by spark plasma sintering with introducing Ti and Al to absorb hexagonal boron nitride (hBN) transformed from cBN. By the results of X-ray diffraction (XRD), Ti and Al reacted with BN and forming TiN, TiB₂, and AlN, which combined cBN as the binder by chemical bonding. The mechanical properties of the prepared composite increased as the increment of sintering temperature. The threshold temperature for preparing composite without hBN phase was at 1400 °C. The composite with optimal mechanical properties was prepared at 1400 °C, and the relative density, the bending strength, hardness, and fracture toughness were 98.9 ± 0.1%, 390.7 ± 4.4 MPa, 14.1 ± 0.5 GPa, and 7.6 ± 0.1 MPa·m^0.5, respectively.     

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%.     

An evaluation of plasma-sprayed coatings based on Al2O3 and Al2O3–13 wt.% TiO2 with bond coat on pure titanium substrate

In this study, the effects of bond coat on the properties of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ coatings, which is plasma sprayed onto a commercial pure titanium substrate with and without Ni–5 wt.% Al (METCO 450 NS) as bond coating layer were investigated in terms of microhardness, bonding strength and surface roughness. Optical and scanning electron microscopy (SEM) examinations revealed that there is a uniform coating layer with no spalling and delamination. However, there is a little amount of porosity. The results indicated that the application of bond coat layer in the plasma spraying of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ on pure titanium substrate has increased the hardness and bonding strength of coatings. While the adhesive bonding is dominant without bond coat, the cohesive bonding is dominant with the application of the bond coating layer. It has been observed that percentage of cohesion strength was about three times higher than that of adhesion strength.     

EELS characterisation of β-tricalcium phosphate and hydroxyapatite

Hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) are of great interest due to their potential application as bone-replacement materials. In particular, composites made of a mixture of these Ca-phosphates revealed improved mechanical properties; however, the reason for this improvement is unknown. Future development and properties enhancement of such bioceramics is linked to the possibility to characterise their particular microstructure. In this context, the ability to quickly identify individual grains of HA and β-TCP within these composites will allow acquiring information about the phase distributions and the phase-boundary microstructure. The aim of the present study is, therefore, to demonstrate that electron energy-loss spectroscopy (EELS) can be successfully employed to differentiate between individual grains of HA and β-TCP. In particular, the analysis of the near-edge structure of the oxygen K-ionisation edge allows detection of a characteristic signal at ca. 536 eV that can be employed as an identification tool for HA. EELS investigations were performed first on as-received and calcined (1000 °C) HA and β-TCP powders and subsequently on pure bulk HA and β-TCP samples sintered at 1250 °C. Finally, this method was successfully applied to a HA/β-TCP (50/50 wt.%) composite sintered at 1250 °C.