Optimisation of the enamelling of an apatite–mullite glass–ceramic coating on Ti<Subscript>6</Subscript>Al<Subscript>4</Subscript>V

Apatite–mullite glass–ceramics (AMGCs) are under investigation as a potential alternative to hydroxyapatite (HA) as a coating for cementless fixation of orthopaedic implants. These materials have tailorable mechanical and chemical properties that make them attractive for use as bioactive coatings. Here, AMGC coatings on Ti₆Al₄V were investigated to determine an improved heat treatment regime using a systematic examination of the different inputs: composition of glass, nucleation hold and crystallisation hold. An upper limit to the heat treatment temperature was determined by the \(\alpha\,+\,\beta\,\longrightarrow\,\beta\) of Ti₆Al₄V at 970°C. The glass composition was modified to produce different crystallisation temperatures and sintering characteristics. A glass was found that is fully crystalline below 970°C and has good sinterability. The effects of different heat treatment time and temperature combinations on the coating and substrate morphologies were examined and the most suitable combination determined. This sample was further investigated and was found to have qualitatively good adhesion and evidence of an interfacial reaction region between the coating and substrate indicating that a chemical reaction had occurred. Oxygen infiltration into the substrate was quantified and the new route was shown to result in a 63% reduction in penetration depth.     

Dielectric properties of Erbium doped CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> prepared by sol–gel self combustion method

The dielectric properties of Erbium doped CaCu₃Ti_(4–x)Er_xO_(12–δ) with x = 0, 0.05, 0.1 were synthesized by the sol–gel self combustion method. XRD (X-ray powder diffraction) analysis confirmed the formation of single-phase material in the samples calcined at 800 °C. Crystal structure does not change on doping with Erbium and it remains cubic in all the three compositions studied. It is found that lattice parameter increases slightly with Erbium doping. The surface morphology of CaCu₃Ti_(4–x)Er_xO_(12–δ) powders sintered at 950 °C in air for 3 h was observed using high resolution—scanning electron microscope and it shows that the grain size is in the range of 1–8 μm for these samples. Energy dispersive X-ray spectroscopy pattern confirmed the presence of Erbium with 1.9 and 4.86 atomic percentages with doping concentration. The dielectric characteristics of CaCu₃Ti_(4–x)Er_xO_(12–δ) were studied by LCR meter in the frequency range (100 Hz–1 MHz) at various temperatures (RT to 500 °C). Interestingly, the dielectric constant increases and dielectric loss had lower values than those of undoped CCTO.     

Electrophoretic deposition of porous CaO–MgO–SiO<Subscript>2</Subscript> glass–ceramic coatings with B<Subscript>2</Subscript>O<Subscript>3</Subscript> as additive on Ti–6Al–4V alloy

The sub-micron glass–ceramic powders in CaO–MgO–SiO₂ system with 10 wt% B₂O₃ additive were synthesized by sol–gel process. Then bioactive porous CaO–MgO–SiO₂ glass–ceramic coatings on Ti–6Al–4V alloy substrates were fabricated using electrophoretic deposition (EPD) technique. After being calcined at 850°C, the above coatings with thickness of 10–150 μm were uniform and crack-free, possessing porous structure with sub-micron and micron size connected pores. Ethanol was employed as the most suitable solvent to prepare the suspension for EPD. The coating porous appearance and porosity distribution could be controlled by adjusting the suspension concentration, applied voltage and deposition time. The heat-treated coatings possessed high crystalline and was mainly composed of diopside, akermanite, merwinite, calcium silicate and calcium borate silicate. Bonelike apatite was formed on the coatings after 7 days of soaking in simulated body fluid (SBF). The bonding strength of the coatings was needed to be further improved.     

Effect of V substitution on microstructure and ferroelectric properties of Bi<Subscript>3.6</Subscript>Ho<Subscript>0.4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by sol–gel method

Bi_3.6Ho_0.4Ti₃O₁₂ and (Bi_0.9Ho_0.1)_4−x/3Ti_3−x V _x O₁₂ (BHTV) (x = 0.3, 1.2, 3.0 and 6.0%) thin films were prepared on Pt/Ti/SiO₂/Si substrates by sol–gel method. The effect of V content on their microstructure and ferroelectric properties were investigated. All the BHTV samples consisted of the single phase of Bi-layered Aurivillius phase. The B-site substitution with high-valent cation of V⁵⁺, in Bi_3.6Ho_0.4Ti₃O₁₂ films, enhanced the remanent polarizations (2P_r) and reduced the coercive field (2E_c). The BHTV film with x = 0.3% exhibited the better electrical properties with 2P_r 45.5 μC/cm², 2E_c 257 kV/cm, good insulting behavior, as well as the fatigue-free characteristic.     

Dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> prepared by sol–gel self combustion technique

The preparation of Calcium copper titanate (CCTO) nanopowder was carried out by a sol–gel self combustion method. The X-ray diffraction analysis indicated that the samples calcined at 800 °C were fully crystallized in the CCTO phase. The results of atomic force microscope showed the particles size of CCTO was in the range of 60–80 nm. The absorption bands corresponding to vibrations of Cu–O, Ti–O–Ti and νCa–O were observed at 512, 450 and 562 cm⁻¹ using FTIR. The samples sintered at 950 °C showed the densities as high as 97% of theoretical density. The grain sizes of sintered pellets were determined by HRSEM. The dielectric properties of prepared samples were studied by LCR meter.     

Wettability of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> by Ag–Cu and Ag–Cu–Ti melts

Recently, the ternary carbide Ti₃SiC₂ has gained much attention due to its unique characteristics combining the properties of metals and ceramics (i.e., a low density, decent thermal and electrical conductivities, an excellent thermal shock resistance, a good machinability, damage tolerance, low friction, and so on). This study describes an investigation of the wettability in high vacuum of bulk Ti₃SiC₂ by a classical braze alloy based on the Ag–Cu–Ti system. Two techniques, i.e., the sessile drop and dispensed drop methods, were utilized. The results indicated that spreading kinetics is controlled by deoxidation kinetics of Ti₃SiC₂ surface under vacuum. The final contact angle on clean Ti₃SiC₂ is very small (~10°), testifying the development of strong, metallic interactions across the liquid–solid interface. The reactivity between the ternary carbide and the liquid phase during isothermal heating at 800 °C was also considered.     

Wear resistance of electrodeposited Ni–B and Ni–B–Si<Subscript>3</Subscript>N<Subscript>4</Subscript> composite coatings

The wear resistance of electrodeposited (ED) Ni–B and Ni–B–Si₃N₄ composite coatings is compared. The effect of incorporation of Si₃N₄ particles in the ED Ni–B matrix on the surface morphology, structural characteristics and microhardness has been evaluated to correlate the wear resistance. The wear mechanism of ED Ni–B and Ni–B–Si₃N₄ composite coatings appears to be similar; both involve intensive plastic deformation of the coating due to the ploughing action of the hard counter disc. However, the extent of wear damage is relatively small for ED Ni–B–Si₃N₄ composite coatings.     

Very low loss tangent and giant dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics prepared by the sol–gel process

The pure phase of CaCu₃Ti₄O₁₂ (CCTO) powder can be successfully synthesized by the sol–gel process. CCTO ceramic samples were synthesized at different sintering temperatures of 1015 and 1050?°C and sintering times of 8 and 10 h. X-ray diffraction results indicated a pure phase for all ceramic samples. Rietveld refinements were adopted for the calculation of lattice constants. Scanning electron microscopy micrographs revealed the effect of sintering conditions on the microstructural evolution of ceramic samples. X-ray absorption near edge spectroscopy was performed to determine the oxidation state of Cu and Ti ions in ceramic samples. The dielectric and non-linear current voltage properties of CCTO ceramic samples were systematically investigated. Interestingly, very low loss tangent (tanδ?<?0.017 at 30?°C and 1 kHz) and giant dielectric constant (ε′?～?10,942) with temperature coefficients less than ±15% in a wide temperature range of ?60 to 125?°C were obtained in the CCTO ceramic sample sintered at 1015?°C for 10 h (CCTO1-10). This suggests a potential use for CCTO1-10 sample in capacitor applications. All CCTO ceramic samples display non-linear characteristic with non-linear coefficient (α) and breakdown field (E _b ) values in the range of 5.69–11.02 and 1415–4294, respectively.     

Effect of Zn<Superscript>2+</Superscript> doping on the structural,magnetic and dielectric properties of MnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> prepared by the sol–gel method

Mn_1?xZn_xFe₂O₄ (x?=?0.2–0.8) ferrite samples were successfully prepared by the sol–gel method. X-ray diffraction study reveals that single cubic spinel phase was formed in Mn_1?xZn_xFe₂O₄ samples. The SEM micrographs revealed that the microstructures change significantly with different Zn²⁺ doping concentration and sintering temperature while the grain size grow up to 9.48 μm for Mn_0.6Zn_0.4Fe₂O₄ sample sintered at 1100 °C. Further, the dielectric and magnetic measurements indicated that both Zn²⁺ doping and sintering temperature could affect both electrical and magnetic parameters such as dielectric constant and saturation magnetization in a great manner. The Mn_0.6Zn_0.4Fe₂O₄ sample sintered at 1100 °C for 8 h is found to show the largest M _s value (77.30 emu/g) in this work. These results indicate that Zn²⁺ doping or sintering temperature can adjust the microstructures, dielectric and magnetic properties of Mn_1?xZn_xFe₂O₄ ferrites.     

High-temperature laser coatings of the ZrB<Subscript>2</Subscript>–MoSi<Subscript>2</Subscript> system on graphite

Coatings of the ZrB₂–MoSi₂ system on graphite (≤ 50 μm thick and 14–15 GPa in hardness) have been produced by pulse laser melting in air of two-layer powder coating with sublayers based on ZrB₂ with additions of ZrSi₂ and SiC. Different coating structures: eutectics of the ZrSiO₄–SiO₂ system based on zircon or a structure of micron-thick fibers of composition Zr(Mo)B₂ are formed depending on the sublayer composition, which controls the coating heat conductivity and accordingly, the crystallization rate of the bath of melt. The prospects of this line of investigations are the improvement of a laser technology of the deposition of high-temperature coating using continuous wave lasers.     

Effect of pH value on the synthesis and characterization of Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>Co<Subscript>0.8</Subscript>Fe<Subscript>0.2</Subscript>O<Subscript>3−δ</Subscript> powders prepared by the citrate–EDTA complexing method

This study reports the successful preparation of potential candidate Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) oxides for intermediate-temperature solid oxide fuel cells (IT-SOFCs) by a combined citrate-ethylenediaminetetraacetic acid (EDTA) complexing method. The resulting crystal properties, chemical composition, conductivity, and electrochemical properties were studied by X-ray diffraction (XRD), inductively coupled plasma mass spectroscopy (ICP-MS), energy dispersive spectrum (EDS), four-point DC measurement and AC impedance. The X-ray diffraction results of all samples with different pH values reveal a basic perovskite structure. Although samples prepared from different pH solutions have a similar structure, their chemical composition and grain morphologies are different. The optimized composition of BSCF is the sample prepared from the precursor solution with a pH value of 6; this produced highest conductivity at 50.2 S/cm at 400 °C, which is 1.3 times higher than the sample prepared from the precursor solution with a pH value of 9. Electrochemical impedance spectra at an intermediate temperature reveal the better electrochemical performance of BSCF electrode prepared from the solution with pH of 6. The lowest polarization resistance values for charge transfer and oxygen diffusion are 0.07 and 0.11 Ω cm² at 800 °C, respectively.     

Plasma-sprayed coatings for oxidation protection on creep of the Ti–6Al–4V alloy

Abstract

The titanium affinity for oxygen is one of the main factors that limit the application of its alloys as structural materials at high temperatures. The objective of this work was to estimate the influence of the plasma-sprayed coatings for oxidation protection on creep of the Ti–6Al–4V alloy, focusing on the determination of the experimental parameters related to the creep stages. Yttria (8 wt.%) stabilized zirconia (YSZ) with a CoNiCrAlY bond coat was air plasma sprayed on Ti–6Al–4V substrates. Constant load creep tests were conducted on the Ti–6Al–4V alloy in air for coated and uncoated samples and in a nitrogen atmosphere for uncoated samples at 600°C to evaluate the oxidation protection on creep of the Ti–6Al–4V alloy. The steady-state creep rate of the coated alloy is smaller than that of the uncoated alloy in air and nitrogen atmosphere. Results about the activation energies and the stress exponent values indicate that the primary and stationary creep, for all test conditions, was probably controlled by dislocation climb. The plasma-sprayed coatings increased the time to rupture and the strain at rupture is smaller than for uncoated samples tested in air.     

Structure,dielectric property and impedance spectroscopy of La<Subscript>2/3</Subscript>Cu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics by sol–gel method

La_2/3Cu₃Ti₄O₁₂ (LCTO) precursor powders were synthesized by the sol–gel method. Effect of sol conditions and sintering process on microstructure and dielectric properties of LCTO powders or ceramics were investigated systematically. The optimum sol conditions for the synthesis of precursor powders were as follows: the Ti⁴⁺ concentration of 1.00 mol/L, the molar ratio of water and titanium of 5.6:1 and the sol pH of 1.0, respectively. After sintered at 1105 °C for 15 h, the LCTO ceramics exhibited more homogeneous microstructure, much higher dielectric constant (ca 09–1.6 × 10⁴) and lower dielectric loss (ca 0.057). The higher dielectric constant of the LCTO ceramics might be due to the internal barrier layer capacitor effect. The LCTO ceramics showed two kinds of conductivity activation energy for grain boundary conductivity from complex impedance analysis. The transition temperature of two activation energy values occured between 170 and 210 °C. The temperature range of 170–210 °C was critical pseudocritical region of the dielectric constant, dielectric loss and activation energy. Furthermore, it was concluded that the grain boundary play an important role for electrical properties.     

Thermal and dielectric properties of the LTCC composites based on the eutectic system BaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The low-temperature co-fired ceramic (LTCC) composites containing quartz based on the eutectic system BaO–Al₂O₃–SiO₂–B₂O₃ are fabricated at the sintering temperature below 980 °C. Preparation process and sintering mechanism were described and discussed, respectively. The results indicated that the addition of quartz to the eutectic system can availably improve dielectric properties of the LTCC composites. In addition, The LTCC composites with optimum compositions, which were obtained by the regulation of an Al₂O₃ content in the composite, can express excellent dielectric properties (permittivity: 5.94, 5.48; loss: 7 × 10⁻⁴, 5 × 10⁻⁴), considerable CTE values (11.7 ppm. °C⁻¹, 10.6 ppm. °C⁻¹) and good mechanical properties (128 MPa,133 MPa).     

Synthesis and piezoelectric properties of (Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>)<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>TiO<Subscript>3</Subscript> ceramics prepared by sol–gel auto-combustion method

In this study, NaNO₃, Bi(NO₃)₃·5H₂O, Ba(NO₃)₂, Ti(OC₄H₉)₄ and citric acid were successfully introduced to fabricate lead-free piezoelectric (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ [NBBT] nanopartical powders by a novel modified sol–gel auto-combustion method. The resultant products were characterized by the X-ray diffraction analysis and transmission electron microscope method. (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ + Mn(NO₃)₂ [NBBTM] can be sintered by the traditional solid-state reaction, and the effects of NBBT doped different amounts of Mn(NO₃)₂ at various sintering temperatures upon phase formation, microstructure as well as piezoelectric properties were further studied. The experimental results show that it was helpful to control their chemical ingredients and microstructure to prepare nanocrystalline single phase NBBT powders. Where is the X-ray diffraction result of the corresponding ceramics to prove the existence of the mixing between rhombohedral and tetragonal phases at the MPB compositions. Doping 0.015 mol% Mn(NO₃)₂ into NBBT at 1,090 °C, piezoelectric constant (d ₃₃) and relative dielectric constant (ε_r) reach the superior value of 159pC/N and 1,304, respectively, and dielectric loss (tan δ) and electromechanical coupling factor (K _t) are 2.5% and 65%, respectively.     

Microstructure and inclusion of Ti–6Al–4V fabricated by selective laser melting

Selective laser melting (SLM) was used in fabricating the dense part from pre-alloyed Ti-6Al-4V powder. The microstructural evolution and inclusion formation of as-fabricated part were characterized in depth. The microstructure was characterized by features of columnar prior β grains and acicular martensite α'. High density defects such as dislocations and twins can be produced in SLM process. Investigations on the inclusions find out that hard alpha inclusion, amorphous CaO and microcrystalline Al₂O₃ are three main inclusions formed in SLM. The inclusions formed at some specific sites on melt pool surface. The microstructural evolution and inclusion formation of as-fabricated material are closely related to the SLM process.     

Chemical interaction of the Ti<Subscript>94</Subscript>Al<Subscript>6</Subscript> and Ti<Subscript>91</Subscript>Al<Subscript>9</Subscript> alloys with ammonia between 150 and 500°C

The chemical interaction of the Ti₉₄Al₆ and Ti₉₁Al₉ alloys with ammonia in the presence of NH₄Cl has been studied at temperatures from 150 to 500°C. The reaction products have been shown to contain nanocrystalline titanium hydride and titanium nitride. The addition of 6–9 at % Al slows down the formation of titanium compounds.     

Influence of defects on mechanical properties of Ti–6Al–4 V components produced by selective laser melting and electron beam melting

This study evaluates the mechanical properties of Ti–6Al–4 V samples produced by selective laser melting (SLM) and electron beam melting (EBM). Different combinations of process parameters with varying energy density levels were utilized to produce samples, which were analyzed for defects and subjected to hardness, tensile, and fatigue tests. In SLM samples, small pores in amounts up to 1 vol.% resulting from an increase in energy density beyond the optimum level were found to have no major detrimental effect on the mechanical properties. However, further increase in the energy density increased the amount of porosity to 5 vol.%, leading to considerable drop in tensile properties. Samples produced using lower-than-optimum energy density exhibited unmelted powder defects, which, even at 1 vol.% level, strongly affected both tensile and fatigue properties. In EBM, insufficient energy input was found to result in large, macroscopic voids, causing serious degradation in all mechanical properties. These findings are helpful in process optimization and standardization of SLM and EBM processes.     

Structure and ferroelectric properties of stoichiometric and Sr-deficient–SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films

SrBi₄Ti₄O₁₅ (SBTi) and Bi-excess and Sr-deficient SBTi (Sr-deficient SBTi, Sr_0.8Bi_4.13Ti₄O₁₅) thin films were deposited on Pt/Ti/SiO₂/Si (100) substrates using a sol–gel method. Structure and electric properties were investigated systematically. These films were random oriented. The remnant polarization (2P _r) of SBTi film was about 25.3 μC/cm², which was larger than the reported value of SBTi thin film. The film with Sr-deficient and Bi-excess composition showed a very large remnant polarization of 36.6 μC/cm². The capacitance–voltage (C–V) characteristics of both the films showed normal ferroelectric behavior. The Curie temperatures of the same Sr-deficient and Bi-excess component ceramics sample increased slightly in comparison with that of SBTi. More importantly, the Sr-deficient and Bi-excess SBTi thin film showed high fatigue resistance against continuous switching up to 4.4 × 10¹⁰ cycles.     

Investigation of charge transport mechanism in semiconducting La<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3</Subscript> manganite prepared by sol–gel method

Here in, we report the charge transport mechanism in semiconducting La_0.5Ca_0.5Mn_0.5Fe_0.5O₃ (LCMFO) polycrystalline material synthesized via sol–gel auto combustion route. X-ray diffraction (XRD) analysis confirmed the orthorhombic phase of the prepared material. Temperature dependent resistivity and impedance spectroscopy measurements have been carried out to probe the dielectric and electrical conduction mechanism which revealed a change of Mott variable range to the small polaronic hopping conduction mechanism around 303 K. The complex impedance and modulus spectra undoubtedly showed the contribution of both grain and grain boundary effect on the conduction properties of LCMFO. An equivalent circuit [(R_gbQ_gb) (R_gQ_g)] model has been used to address the electrical parameters associated with the different phases (grains and grain boundaries) having different relaxation times. The values of resistances of two phases obtained after fitting the equivalent circuit in the nyquist plot have been analyzed which confirmed the change of conduction mechanism around 303 K. The resultant change in conduction mechanism is also supported by the conductivity plots.