Selective laser sintering of barium titanate–polymer composite films

A selective laser sintering process has been used to consolidate electro-ceramic thin films on silicon substrates. Methods of forming pre-positioned layers of barium titanate were investigated by spin-coating the feedstock powder mixed with a commercial polymer photo-resist. The ceramic–polymer composite was deposited directly onto a nickel film which was evaporated onto a silicon substrate, pre-oxidised to form an electrically insulating layer. A range of laser processing parameters was identified in which consolidated barium titanate layers could be formed. The laser power was found to be more influential in forming sintered microstructures than laser exposure time. The microstructure of barium titanate films is sensitive to the SLS laser-processing conditions, with the optimum laser powers for the processing of the BaTiO₃–polymer found to be in the range 17–20 W. This article highlights the possibility of using ‘direct write’ techniques to produce piezoelectric materials upon silicon substrates.     

Pullulan–nanofibrillated cellulose composite films with improved thermal and mechanical properties

Novel bionanocomposite films with improved thermal and mechanical properties, were prepared by casting water-based suspensions of pullulan and nanofibrillated cellulose. The effect of the addition of glycerol, as a plasticizer, on the properties of the materials was also evaluated. The ensuing materials were characterized in terms of morphology, thermal stability, crystalline structure and mechanical properties. All bionanocomposites were very homogeneous, translucent and showed considerable improvements in thermal stability (increments of up to 20 °C in the degradation temperature) and mechanical properties (increments of up to 5500% and 8000% in the Young’s modulus and tensile strength, respectively, for films plasticized with glycerol) when compared to the unfilled pullulan films. Additionally, these novel bionanocomposite could be labeled as sustainable materials since they were prepared entirely from renewable resources and through a green approach.     

Fabrication and mechanical properties of β-TCP pieces by gel-casting method

In the present work, dense β-TCP ceramics were fabricated by gel-casting method. The effects of the solids loading on the rheological behavior of β-TCP slurries were investigated. When the concentration of the slurries was increased from 40 to 60 vol.%, the compressive strength of green pieces was raised from 12.4 ± 1.1 to 41.2 ± 2.3 MPa, and flexural strength from 9.4 ± 0.4 to 16.3 ± 0.9 MPa. The density of the final specimens was 97.4% of the theoretical density after pressureless sintering at 1100 °C. The compressive strength, flexural strength, elasticity modulus and the fracture toughness of the sintered pieces were 291 ± 15 MPa, 93.0 ± 8.7 Mpa, 72.4 ± 7.5 GPa and 0.92 ±0.04 Mpa·m^0.5 respectively. SEM images show a compact and uniform microstructure; XRD and FTIR determined the phase and the radical before and after sintering.     

Correlation between properties and microstructure of laser sintered porous β-tricalcium phosphate bone scaffolds

Abstract

A porous β-tricalcium phosphate (β-TCP) bioceramic scaffold was successfully prepared with our homemade selective laser sintering system. Microstructure observation by a scanning electron microscope showed that the grains grew from 0.21 to 1.32 μm with the decrease of laser scanning speed from 250 to 50 mm min^?1. The mechanical properties increased mainly due to the improved apparent density when the laser scanning speed decreased to 150 mm min^?1. When the scanning speed was further decreased, the grain size became larger and the mechanical properties severely decreased. The highest Vickers hardness and fracture toughness of the scaffold were 3.59 GPa and 1.16 MPa m^1/2, respectively, when laser power was 11 W, spot size was 1 mm in diameter, layer thickness was 0.1–0.2 mm and laser scanning speed was 150 mm min^?1. The biocompatibility of these scaffolds was assessed in vitro with MG63 osteoblast-like cells and human bone marrow mesenchymal stem cells. The results showed that all the prepared scaffolds are suitable for cell attachment and differentiation. Moreover, the smaller the grain size, the better the cell biocompatibility. The porous scaffold with a grain size of 0.71 μm was immersed in a simulated body fluid for different days to assess the bioactivity. The surface of the scaffold was covered by a bone-like apatite layer, which indicated that the β-TCP scaffold possesses good bioactivity. These discoveries demonstrated the evolution rule between grain microstructure and the properties that give a useful reference for the fabrication of β-TCP bone scaffolds.     

The improved mechanical properties of Al matrix composites reinforced with oriented β-Si3N4 whisker

The β-Si₃N₄ whiskers (β-Si₃N₄w) reinforced Al matrix composites were first fabricated by hot pressing, then treated through hot extrusion. The microstructure characterization demonstrated the preferred orientations of both β-Si₃N₄w and Al grains in the as-extruded composites. It indicated that β-Si₃N₄w were aligned along the extrusion direction and Al grains exhibited a distinct <111>_Al texture. The interface between β-Si₃N₄w and Al was in a good bonding status without voids and reaction products. Effects of extrusion process on the mechanical properties of composites were also investigated. The results indicated the extrusion process had a prominent strengthening effect on the mechanical properties of composites. The maximum yield strength and ultimate tensile strength of composites reached up to 170 and 289 MPa, respectively, accompanied by a 12.3% elongation at fracture when the whisker fraction was 15 vol.%. This improvement was collectively attributed to the densification of composites, the strong interface, and the preferred orientation inside composites. The yield strength of the composites reinforced with 5 vol.% β-Si₃N₄w corresponded well with the theoretical value from different strengthening mechanisms.     

Preparation, characterization and mechanical performance of dense β-TCP ceramics with/without magnesium substitution

Beta-tricalcium phosphate (beta-TCP) powder was prepared by a two-step process: wet precipitation of apatitic tricalcium phosphate [Ca(9)(HPO(4))(PO(4))(5)(OH)] (beta-TCP 'precursor') and calcination of the precursor at 800 degrees C for 3 h to produce beta-TCP. Magnesium-substituted tricalcium phosphate (beta-TCMP) was produced by adding Mg(NO(3))(2) . 6H(2)O into Ca(NO(3))(2) solution as Mg(2+) source before the precipitation step. The transition temperature from beta-TCP to alpha-TCP increases with the increase of Mg(2+) content in beta-TCMP. beta-TCMP with 3 mol.% Mg(2+) has beta-TCP to alpha-TCP transition temperature above 1,300 degrees C. Dense beta-TCMP (3 mol.% Mg(2+)) ceramics ( approximately 99.4% relative density) were produced by pressing the green bodies at 100 MPa and further sintering at 1,250 degrees C for 2 h. The average compressive strength of dense beta-TCP ceramics sintered at 1,100 degrees C is approximately 540 MPa, while that of beta-TCMP (3 mol.% Mg(2+)) ceramics is approximately 430 MPa.     

Sintering and mechanical properties of β-wollastonite

Detailed microstructural studies have been carried out on porous -wollastonite (CaSiO₃) ceramics with 40–60% of the theoretical density. Xonotlite (Ca₆Si₆O₁₇(OH)₂) was used as starting material, and the reaction and sintering behaviour were systematically examined in the range 800–1200 °C in air. Analysis of the mechanical properties showed that the strength degradation of -wollastonite ceramics was certainly induced by the change of microstructure. Isothermal annealing at 1100 °C, however, did not preferentially affect the microstructure or the mechanical properties of sintered -wollastonite. These observations lead to the conclusion that the measured bending strength and Vickers hardness of porous -wollastonite ceramics can be substantially modified and improved by controlling the microstructure, in particular due to the shape of randomly oriented grains in the matrix.     

Scavenging phenomenon and improved electrical and mechanical properties of polyaniline–divinylbenzene composite in presence of MWCNT

A semi-doped polyaniline (PANI)–dodecylbenzenesulfonic acid (DBSA) complex is added with a suspension of multiwall carbon nanotubes (MWCNT)–divinylbenzene (DVB) to prepare PANI–MWCNT based thermosetting conductive resin system. Firstly, unreinforced nanocomposites with various loading of MWCNT are prepared. Continuous improvement in the electrical conductivity is observed with increasing MWCNT loading in the composite, while improvement in the mechanical properties is observed only up to 0.2 wt% MWCNT loading. On further MWCNT loading, the decrease in mechanical properties is observed. Flexural strength increased by 18% with 0.2 wt% of MWCNT in the unreinforced nanocomposite while electrical conductivity increased continuously to 0.68 S/cm (at 0.5 wt% of MWCNT loading) from 0.25 S/cm (neat sample). DSC and TGA analysis show that MWCNT effectively contributed to enhance the scavenging effect of PANI, affecting degree of DVB polymerization at higher loading of MWCNT. Samples were characterized by FTIR analysis. DMA analysis is also performed to understand the mechanical behavior of the cured unreinforced nanocomposite under dynamic loading. SEM observation has been employed to understand the dispersion behavior of MWCNT into the matrix. PANI-wrapping behavior on MWCNT is observed from the SEM images. Wrapping of PANI on MWCNT increased doping state and surface area of PANI which subsequently contribute to the increased scavenging behavior of PANI at higher MWCNT loading. A structural thermosetting nanocomposite with electrical conductivity of 0.68 S/cm, flexural modulus of 1.87 GPa and flexural strength up to 35 MPa is prepared. In addition, PANI–DBSA/DVB matrix with MWCNT is also used to impregnate carbon fabrics to prepare highly conductive CFRPs. A CFRP with 1.67 S/cm electrical conductivity in through-thickness direction and 328 MPa flexural strength is obtained with the addition of 0.2 wt% MWCNT into the resin system.     

Synthesis of bioactive β-TCP coatings with tailored physico-chemical properties on zirconia bioceramics

The objective of this work was to develop a synthesis procedure for the deposition of β-TCP coatings with tailored physico-chemical properties on zirconia bioceramics. The synthesis procedure involved two steps: (i) a rapid wet-chemical deposition of a biomimetic CaP coating and (ii) a subsequent post-deposition processing of the biomimetic CaP coating, which included a heat treatment between 800 and 1200 °C, followed by a short sonication in a water bath. By regulating the heating temperature the topography of the β-TCP coatings could be controlled. The average surface roughness (R_a) ranged from 42 nm for the coating that was heated at 900 °C (TCP-900) to 630 nm for the TCP-1200 coating. Moreover, the heating temperature also affected the dissolution rate of the coatings in a physiological solution, their protein-adsorption capacity and their bioactivity in a simulated body fluid.     

Preparation of β-FeSi2 thermoelectric material by laser sintering

Laser sintering has been applied for preparing β-FeSi₂ based thermoelectric alloy for the first time. Effects of laser sintering time on alloying, phase transformation and microstructure of FeSi₂ were investigated by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). Effects of annealing temperature and time on phase transformation were also studied through Seebeck coefficients. The results show that for 90 s laser-sintered samples, it takes only 15 h to obtain β phase under Ar atmosphere followed by an annealing at 1073 K. These samples exhibit homogeneous microstructure with average grain size of less than 5 μm. A maximum Seebeck coefficient at room temperature could reach 115 μV/K. It indicates that laser sintering could be an alternate faster preparation method to generate high quality β-FeSi₂ thermoelectric material with little contamination due to its advantages of rapid heating rate, high cooling rate and rapid solidification.     

High strain recovery with improved mechanical properties of gelatin–silica aerogel composites post-binding treatment

Silica aerogels are very light and highly porous materials that are intriguingly and complexly networked with large internal surface area, high hydrophobicity with extremely low density and thermal conductivity. These features make them ideal choice for applications as thermal and acoustics insulators or as optical, electrical, and energy storing devices. However, their exploitation for structural applications is primarily inhibited by their brittleness. The brittleness of the silica aerogels makes their processing and handling difficult. Volumetric shrinkage occurs, which becomes more apparent at elevated temperatures. While there are hybrid silica aerogels doped with materials such as polymer, ceramics, metals in the market, the improvements in the mechanical properties are compromised with tremendous increase in density and reduction in the insulation performance. Post-synthesis binding treatment of silica aerogels composites are not extensively explored due to the chemically inert trimethylsilyl (TMS) terminal groups on the surface of the hydrophobic silica aerogels. This paper discusses a unique fabrication method of developing a ductile silica aerogel composite solid via post-synthesis binding treatment. Gelatin–silica aerogel (GSA) and GSA–sodium dodecyl sulfate (SDS) composite blocks were produced by mixing hydrophobic aerogel granulates in a gelatin–SDS foamed solution by frothing method. The entire fabrication process and grounds for using a controlled % of gelatin as the main binder and SDS as an additive are explained. The compression testing of the blocks is presented. The associated strain recovery—an unusual phenomenon with brittle silica aerogels, observed upon unloading is highlighted and studied. The microstructure and surface characterization of these composites was examined via FESEM/EDX and XPS/ESCA, respectively. The dependency of process variables involved were analyzed through analysis of variance (ANOVA) model. Empirical models that relate the composition of gelatin, aerogel, and SDS to achieve the optimal strain recovery with the associated compressive modulus and strength and density are established. The transition from brittleness to ductility is measured in terms of compressive stress versus strain behavior for various mass fractions of gelatin and SDS. The test data presented indicate analogous behavior of these to creep-like behavior of a material typically identified as the primary, secondary, and tertiary stages. The rationale and mechanisms behind such creep-like three stages are explained using schematic diagrams.     

The growth of stem cells within β-TCP scaffolds in a fluid-dynamic environment

A three-dimensional dynamic perfusion system was developed to provide mass transport and nutrient supply to permit the cell proliferation during the long-term culture inside a β-tricalcium phosphate (β-TCP) scaffold. Also the flow field throughout the scaffold was studied. The porous cylindrical scaffold with a central channel was seeded with the sheep mesenchymal stem cells (MSCs). Then the cell-seeded scaffolds were continuously perfused with the complete α-MEM medium by a peristaltic pump for 7, 14 and 28 days, respectively. Histological study showed that the cell proliferation rates were different throughout the whole scaffolds and the different cell coverage was shown in different positions of the scaffold. Unoccupied spaces were found in many macropores. A computational fluid dynamics (CFD) modeling was used to simulate the flow conditions within perfused cell-seeded scaffolds to give an insight into the mechanisms of these cell growth phenomena. Relating the simulation results to perfusion experiments, the even fluid velocity (approximately 0.52 mm/s) and shear stress (approximately 0.0055 Pa) were found to correspond to increased cell proliferation within the cell–scaffold constructs. Flow speeds were between 0.25 and 0.75 mm/s and shear stresses were between 0.003 and 0.008 Pa in approximately 75% of the regions. This method exhibits novel capabilities to compare the results obtained for different perfusion rates or different scaffold microarchitectures. It may allow specific fluid velocities and shear stresses to be determined to optimize the perfusion flow rate, porous scaffold architecture and distribution of in vitro tissue growth.     

Preparation and in vitro evaluation of mesoporous hydroxyapatite coated β-TCP porous scaffolds

A mesoporous hydroxyapatite (HA) coating was prepared on a β-tricalcium phosphate (β-TCP) porous scaffold by a sol-gel dip-coating method using the block copolymer Pluronic F127 (EO₁₀₆PO₇₀EO₁₀₆) as the template. For application as a bone graft, in vitro cell response and bone-related protein expression of mesoporous HA coated β-TCP scaffold were investigated, using the non-mesoporous HA coated scaffold as the control group, to evaluate the influence of the mesoporous structure on the biological properties of HA coating. It was found that the increased surface area of the mesoporous HA coating greatly affected the response of MC3T3-E1 osteoblasts and the expression of proteins. An enzyme-linked immunosorbent assay recorded a significantly higher expression of alkaline phosphatase (ALP) and bone sialoprotein (BSP) in the mesoporous group than those in the control group (*p < 0.05) after different incubation periods. The introduction of mesopores enhanced the expression of ALP and BSP in the cells grown on the mesoporous HA coatings, on the premise of maintaining the protein expression in a sequence to ensure the correct temporo-spatial expression in osteogenesis. These results indicated that the mesoporous HA coating would provide a good environment for cell growth, suggesting that it could be used as the coating material for the surface modification of the tissue engineering scaffolds.     

The healing of critical-size calvarial bone defects in rat with rhPDGF-BB, BMSCs, and β-TCP scaffolds

Platelet-derived growth factor-BB (PDGF-BB) plays important roles in regenerating damaged tissue. In this study we investigated the effects of a tissue-engineered bone combined with recombinant human PDGF-BB (rhPDGF-BB), bone marrow stem cells (BMSCs) and β–tricalcium phosphate (β-TCP) to repair critical-size calvarial bone defects in rat. Proliferation and osteogenic differentiation of BMSCs treated with different concentration rhPDGF-BB (0, 10, and 50 ng/ml) was evaluated by MTT, alkaline phosphatase (ALP) activity, alizarin red staining and real-time quantitative PCR (RT-qPCR) analysis of osteogenic gene. BMSCs were then combined with rhPDGF-BB-loaded β-TCP and transplanted into 5 mm calvarial bone defects. The new bone formation and mineralization was evaluated by micro-computerized tomography (Micro-CT) and histological analysis at week 8 after operation. It was observed that the proliferation of BMSCs treated with rhPDGF-BB was enhanced with a time- and dose- dependent manner. There were increased ALP activity, mineralized deposition and elevated mRNA levels of osteogenic gene for BMSCs treated with rhPDGF-BB, particularly in the 50 ng/ml group. Histological analysis showed new bone formation and mineralization in the rhPDGF-BB/BMSCs/β-TCP group was significantly higher than BMSCs/β-TCP, rhPDGF-BB/β-TCP, and β-TCP alone group (P < 0.05). In conclusion, rhPDGF-BB/BMSCs/β-TCP is a promising tissue-engineered bone for craniofacial bone regeneration.     

Fabrication of biodegradable nano-sized β-TCP/Mg composite by a novel melt shearing technology

Biodegradable magnesium-matrix composites have attracted increasing interest for application in implant material fields. In this study, a new type of nano-sized β-tricalcium phosphate (β-TCP)/Mg–3Zn–Ca composite was proposed and produced using a novel melt shearing technology combined with high-pressure die casting (HPDC) process. The effect of the mixing methods on the distribution of β-TCP particles was investigated. Microstructure evolution during solidification process was analysed and the mechanical properties of the composite were also evaluated. Compared with the conventional mechanical stirring, the agglomerate phenomenon of the β-TCP particles in the matrix can be decreased by using the high shear unit and further decreased by melt shearing in the MCAST unit. The results also showed that the main constitutes in the matrix of the β-TCP/Mg–3Zn–1Ca composite are α-Mg and Ca₂Mg₆Zn₃ phase and most of the β-TCP particles are adjacent to the eutectic Ca₂Mg₆Zn₃ phase around the grain boundary. The average Vickers hardness, yield strength (0.2% YS), ultimate tensile strength (UTS), elastic modulus and elongation of as-cast of this composite are 79.0, 125.4 MPa, 150.0 MPa, 45.3 GPa and 2.85%, respectively.     

Mechanical alloying process and mechanical properties of Cu–SiCp composite

Abstract

A composite of copper powder and SiC particle reinforcement was prepared by mechanical ball milling and subsequent sintering. Proper choice of processing parameters ensured a homogenous distribution of SiC particles in the copper matrix. Microstructure, powder morphology and mechanical properties of the composite were investigated as a function of milling time. With increasing milling time, the dentritic copper powder became flattened, which subsequently became spherical shaped. Mechanical properties of the composites change with the distribution of SiC.     

Effect of calcinations of starting powder on mechanical properties of hydroxyapatite–alumina bioceramic composite

The effect of calcinations of starting powder on the mechanical properties of hydroxyapatite (HA)-based bioceramic composite was investigated. The calcinations of HA powder in air at 900 °C increased the crystallinity as well as the size of the powder. Ball milling after the calcinations was effective in eliminating large agglomerates in the powder. When the powder was mixed with reinforcing Al₂O₃ powder, the mixture became fine and homogeneous. The flexural strength of HA–Al₂O₃ composite was increased by the calcinations processes at all the Al₂O₃ concentration. However, the fracture toughness was not much influenced by the calcinations. These results lead to the conclusion that the calcinations process effectively reduced the critical flaw size in the body by removing the agglomerates in the HA powder.     

Dielectric,mechanical and thermal properties of novel core–shell CuPc@MWCNTs/PEN composite films

In this work, multiwalled carbon nanotubes (MWCNTs) were successfully enwrapped by a thin layer of tetra-nitrophthalocyanine copper (CuPc) via solvent-thermal method. EDS spectrum shows that the hybrid materials are mainly composed of C, Cu, N and O elements. TEM images exhibit that the MWCNT was wholly coated with a layer of CuPc and micro-nanoscale core–shell CuPc@MWCNTs were formed. FTIR reveals the detailed chemical groups of micro-nanoscale core–shell CuPc@MWCNTs. Thereafter, CuPc@MWCNTs/polyarylene nitrile ethers (PEN) composite films were prepared via solution-casting method. The CuPc@MWCNTs/PEN composite films possess excellent thermal and mechanical properties endowed by PEN matrix. The glass transition temperature of the composite films is about 175 °C and the initial decomposition temperature is in the range of 494–499 °C. Besides, the tensile modulus of the composite films is above 70 MPa. Furthermore, the dielectric constant of the composite film with 5.0 wt% CuPc@MWCNTs loading is 31 at 50 Hz while the dielectric loss is 0.58 at 50 Hz.