羟基磷灰石/外消旋聚乳酸复合材料的制备、力学性能及体外降解

采用液相吸附法制备了羟基磷灰石/外消旋聚乳酸[hydroxyapatite/poly-D,L(racemic)lactic acid,HA/PDLLA]复合材料,通过材料实验机和体外模拟试验研究了复合材料的力学性能和体外降解性能.对材料的力学测试表明,由于加入了质量分数为10%的HA颗粒,复合材料的力学性能得到了改善,复合材料的弯曲强度达146.2 MPa,弯曲模量为2.5 GPa,与纯PDLLA材料相比,弯曲强度提高了9.4 MPa,弯曲模量提高了0.2 GPa,同时其拉伸强度下降并不明显.体外降解模拟试验结果表明,HA含量为10%的复合材料在前6周的质量损失小于1%,在第12周的最终质量损失为5.4%,其在降解中后期的质量损失比纯PDLLA材料低约2%～3%.     

Poly(para‐dioxanone)/poly(D,L‐lactide) blends compatibilized with poly(D,L‐lactide‐co‐para‐dioxanone)

The effect of poly(D ,L ‐lactide‐co‐para‐dioxanone) (PLADO) as the compatibilizer on the properties of the blend of poly(para‐dioxanone) (PPDO) and poly(D ,L ‐lactide) (PDLLA) has been investigated. The 80/20 PPDO/PDLLA blends containing from 1% to 10% of random copolymer PLADO were prepared by solution coprecipitation. The PLADO component played a very important role in determining morphology, thermal, mechanical, and hydrophilic properties of the blends. Addition of PLADO into the blends could enhance the compatibility between dispersed PDLLA phase and PPDO matrix; the boundary between the two phases became unclear and even the smallest holes were not detected. On the other hand, the position of the T_g was composition dependent; when 5% PLADO was added into blend, the T_g distance between PPDO and PDLLA was shortened. The blends with various contents of compatibilizer had better mechanical properties compared with simple PPDO/PDLLA binary polymer blend, and such characteristics further improved as adding 5% random copolymers. The maximum observed tensile strength was 29.05 MPa for the compatibilized PPDO/PDLLA blend with 5% PLADO, whereas tensile strength of the uncompatibilized PPDO/PDLLA blend was 14.03 MPa, which was the lowest tensile strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Injection‐molded high‐density polyethylene–hydroxyapatite–aluminum oxide hybrid composites for hard‐tissue replacement: Mechanical,biological, and protein adsorption behavior

In this article, we report the mechanical and biocompatibility properties of injection‐molded high‐density polyethylene (HDPE) composites reinforced with 40 wt % ceramic filler [hydroxyapatite (HA) and/or Al₂O₃] and 2 wt % titanate as a coupling agent. The mechanical property measurements revealed that a combination of a maximum tensile strength of 18.7 MPa and a maximum tensile modulus of about 855 MPa could be achieved with the injection‐molded HDPE–20 wt % HA–20 wt % Al₂O₃ composites. For the same composite composition, the maximum compression strength was determined to be 71.6 MPa and the compression modulus was about 660 MPa. The fractrography study revealed the uniform distribution of ceramic fillers in the semicrystalline HDPE matrix. The cytocompatibility study with osteoblast‐like SaOS2 cells confirmed extensive cell adhesion and proliferation on the injection‐molded HDPE–20 wt % HA–20 wt % Al₂O₃ composites. The cell viability analysis with the 3(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay revealed a statistically significant difference between the injection‐molded HDPE–20 wt % HA–20 wt % Al₂O₃ composites and sintered HA for various culture durations of upto 7 days. The difference in cytocompatibility properties among the biocomposites is explained in terms of the difference in the protein absorption behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

EVALUATION OF A COMPOSITE BASED ON HIGH-DENSITY POLYETHYLENE FILLED WITH SURFACE-TREATED HYDROXYAPATITE

Summary  Composites properties are directly related to the degree of interaction between the plastic matrix and the inorganic filler. In the present work, the improvement of the composite’s properties by means of the addition of surface-treated and untreated hydroxyapatite (STHA and HA, respectively) was studied. An ethylene-acrylic acid copolymer was melt blended with high-density polyethylene and HA (HDPE/HA/EA). A surface treatment was performed using an ethylene-acrylic acid (EA) copolymer for STHA₁ and acrylic acid (AA) for STHA₂. High-density polyethylene (HDPE) was also tested. STHA₁ and STHA₂ composites exhibited Young’s modulus values (556 and 558 MPa, respectively) 22 % higher than that of HDPE/HA (455 MPa) and 8 % higher than that of HDPE/HA/EA (520 MPa). Additionally, STHA composites showed both yield stress and strain (σ_STHA1= 23 MPa; ε_STHA1= 9 %; σ_STHA2= 22 MPa; ε_STHA2= 10 %) having a remarkably different behavior from that of the HA composites, which showed no yielding at all. TEM micrographs showed better filler dispersion when surface treatment was applied to HA. Yet, the presence of EA copolymer exhibited a poorer thermal stability. The crystallinity degree as well as the crystallization and melting temperatures showed no significant variation. Regarding in vitro evaluation, composites with HA and EA copolymer proved to have better cell adhesion at early stages. The results of the STHA composites could be attributed to the electrostatic interactions taking place between the ethylene-acrylic acid copolymer and the polar groups of the HA.     

Development of hydroxyapatite nanoparticles reinforced chlorinated acrylonitrile butadiene rubber/chlorinated ethylene propylene diene monomer rubber blends

Hydroxyapatite nanoparticles (HA) reinforced polymer blend based on chlorinated nitrile rubber (Cl-NBR) and chlorinated ethylene propylene diene monomer rubber (Cl-EPDM) were prepared. Resulting blend composites were analyzed with regard to their rheometric processing, crystallinity, glass transition temperature (T_g), mechanical properties, oil resistance, AC conductivity, and transport behavior. The decrease in optimum cure time with the addition of HA is more advantageous for the development of products from these blend nanocomposites. The XRD, FTIR, and SEM confirmed the attachment and uniform dispersion of HA nanoparticles in the Cl-NBR/Cl-EPDM blend. The good compatibility between polymer blend and nanoparticles was also deduced by the formation of spherically shaped HA particles in the blend matrix determined by TEM analysis. DSC analysis showed an increase in T_g of the blend with the filler loading. The addition of HA particles to the blend produced a remarkable increase in tensile and tear strength, hardness, AC conductivity, abrasion, and oil resistance. The diffusion of blend composites was decreased with an increase in penetrant size. The diffusion mechanism was found to follow an anomalous trend. Among the blend composites, the sample with 7 phr of HA not only showed good oil and solvent resistance but also a remarkable increase in AC conductivity and mechanical properties.     

Properties of novel PMMA‐co‐EHA bone cements filled with hydroxyapatite

To design bone cements with predictable intraoperative and postoperative behavior, researchers must understand how cement formulations affect the polymerization reaction and specially the properties of the end product. In this study, a bioactive filler (commercial hydroxyapatite, HA) was incorporated into poly(methyl methacrylate)‐co‐ethyl hexyl acrylate (PMMA‐co‐EHA) matrices to prepare new bone cement formulations. The new PMMA‐co‐EHA/HA composites were obtained by varying the relative contents of the monomers, MMA, and EHA. The resulting composites were evaluated in terms of the curing parameters, water uptake and weight loss in phosphate buffer solution and mechanical properties. The results obtained showed that incorporation of 25% HA particles induced major changes in the final properties of the bone cements comparing with the unfilled parent matrices. In particular, the peak temperature decreased and the setting time and the bending elastic modulus increased in all formulations containing HA particles. Composites with low EHA content exhibited a decrease in strength after HA incorporation, which was attributed to the poor interfacial adhesion between the components of the composites. Additionally, the immersion results showed that the amount of 25% HA (regarding the total mass) in the composites was not enough to induce in vitro bioactive properties in the materials. POLYM. COMPOS., 35:759–767, 2014. © 2013 Society of Plastics Engineers     

Microstructures and mechanical properties of B4C–SiC and B4C–SiC–TiB2 ceramic composites fabricated by hot pressing

Boron carbide (B₄C) ceramic composites with excellent mechanical properties were fabricated by hot-pressing using B₄C, silicon carbide (SiC), titanium boride (TiB₂), and magnesium aluminum silicate (MAS) as raw materials. The influences of SiC and TiB₂ content on the microstructural evolution and mechanical properties of the composites were systematically investigated. The mechanism by which MAS promotes the sintering process of composites was also investigated. MAS exists in composites in the form of amorphous phase. It can effectively remove the oxide layer from the surface of ceramic particles during the high temperature sintering process. The typical values of relative density, hardness, bending strength, and fracture toughness of B₄C–SiC–TiB₂ composites are 99.6%, 32.61 GPa, 434 MPa, and 6.20 MPa m^1/2, respectively. Based on the microstructure observations and finite element modeling, the operative toughening mechanism is mainly attributed to the crack deflection along the grain boundary, which results from the residual stress field generated by the thermal expansion mismatch between B₄C and TiB₂ phase.     

Additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic composites

A material extrusion (MEX) technology has been developed for the additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic (C_f/SiC) composites. By comparing and analyzing the rheological properties of the slurries with different compositions, a slurry with a high solid loading of 48.1 vol% and high viscosity was proposed. Furthermore, several complex structures of C_f/SiC ceramic composites were printed by this MEX additive manufacturing technique. Phenolic resin impregnation–carbonization process reduces the apparent porosity of the green body and protects the C_f. Finally, the reactive melting infiltration (RMI) process was used to prepare samples with different C_f contents from 0 to 2 K (a bundle of carbon fibers consisting of 1000 fibers). Samples with C_f content of 1 K show the highest bending strength (161.6 ± 10.5 MPa) and fracture toughness (3.72 ± 0.11 MPa·m^1/2) while the thermal conductivity of the samples with the C_f content of 1 K reached 11.0 W/(m·K). This study provides a strategy to prepare C_f/SiC composites via MEX additive manufacturing and RMI.     

Processing and mechanical performance of 3D Cf/SiCN composites prepared by polymer impregnation and pyrolysis

The processing of 3D carbon fiber reinforced SiCN ceramic matrix composites prepared by polymer impregnation and pyrolysis (PIP) route was improved, and factors that determined the mechanical performance of the resulting composites were discussed. 3D C_f/SiCN composites with a relative density of ∼81% and uniform microstructure were obtained after 6 PIP cycles. The optimum bending strength, Young's modulus and fracture toughness of the composites were 75.2 MPa, 66.3 GPa and 1.65 MPa m^1/2, respectively. The residual strength retention rate of the as-pyrolyzed composites was 93.3% after thermal shock test at ΔT = 780 °C. It further degraded to 14.6% when the thermal shock temperature difference reached to 1180 °C. The bending strength of the composites was 35.6 MPa after annealing at 1000 °C in static air. The deterioration of the bending strength should be attributed to the strength degradation of carbon fibers and decomposition of interfacial structure.     

Microstructure and mechanical properties of B4C–TiB2 ceramic composites prepared via a two-step method

B₄C–TiB₂ ceramic composites were fabricated by a two-step method. First, B₄C–TiB₂ composite powders were synthesized from TiC–B powder mixtures at 1400 ℃, then mixed with commercial B₄C powders by ball milling and the B₄C–TiB₂ ceramic composites were prepared by hot pressing at 1950 ℃. This two-step method not only effectively refined TiB₂ grains, but also allowed the composition of the composites to be freely designed. The microstructure and mechanical properties of the composites were investigated. The results showed that the B₄C–TiB₂ ceramic composite with a 10 wt% TiB₂ content obtained the ideal comprehensive performance, with a volume density, Vickers hardness, bending strength, and fracture toughness of 2.61 g/cm³, 35.3 GPa, 708 MPa, and 5.82 MPa m^1/2, respectively. The advantages of the in-situ reaction process were fully exerted by the two-step method, which made a remarkable contribution to the excellent properties of B₄C–TiB₂ ceramic composites.     

Hydroxyapatite nanocomposites: Synthesis,sintering and mechanical properties

Two different hydroxyapatite based composites reinforced by oxide ceramic (20 wt%) nano crystals were synthesized by high-energy ball milling and sintered by pressure less technique. Alumina and titania nanoparticles as secondary phases improved densification and mechanical behavior of apatite and postponed its decomposition to the tricalcium phosphate (TCP) phases at elevated temperatures. Increasing the relative density of apatite using nano reinforcements leads to enhance the bending strength by more than 40% and 27% (as compared to the pure HA) and increase the hardness from 2.52 to 5.12 (Al₂O₃ composite) and 4.21 (TiO₂ addition) GPa, respectively. Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction spectroscopy were employed to study morphologies, fracture surfaces and phase compositions, respectively. The morphological study and micro structural analysis confirm the X-ray diffraction and relative density diagrams.     

The effect of whisker orientation in SiC whisker-reinforced Si3N4 ceramic matrix composites

Si₃N₄ ceramic matrix composites reinforced by nearly unidirectionally aligned SiC whiskers have been prepared by extrusion and hot pressing. Unlike the case in traditional Si₃N₄ ceramic matrix composites reinforced by random SiC whiskers, the mechanical properties of the composites exhibit a significant dependence on whisker orientation. In the direction of whisker alignment for SiC(w)/Si₃N₄ composites, increments in bending strength and fracture toughness of 200 MPa and 3 MPa·m^1/2 are obtained respectively, compared to the values in the direction perpendicular to whisker alignment. Based on microscopic fractographic observation and micromechanics analyses, the effects of whisker orientation on toughening mechanisms are discussed. The results indicate that the whisker orientation, θ, is a decisive factor for the essential toughening mechanisms of whiskers. Only in the case of small θ and weak interface can whisker pullout occur, and whisker has maximum toughening effect. The results show that effects of whisker strengthening and toughening can be improved simultaneously through whisker oriented alignment. ©     

Design of Janus particles based on silica@polystyrene and their compatibilization on poly(p-dioxanone)/poly(lactic acid) composites

The compatibility of poly(p-dioxanone) (PPDO) and poly(lactic acid) (PLA) is very important when they are blended. Herein, three kinds of snowman-like Janus particles (JPs) with different hydrophilic–lipophilic balance (HLB) were prepared by one-pot method by adjusting the surficial functional groups of polystyrene (PS) side and used as the compatibilizer of PPDO/PLA composites. JPs self-assemble at the cell-structure PPDO/PLA interface, which provides channels for the migration of PPDO. The silica (SiO₂) side forms hydrogen bond with PLA, and the PS side forms hydrophobic action with PPDO. Therefore, JPs improve interfacial adhesion and suppress phase separation. Among the three JPs, silica@polystyrene-graft-polymethylmethacrylate (SiO₂@PS-PMMA) possesses the most excellent interfacial behavior because its HLB value is similar to that of PPDO/PLA composites. Tensile strength was increased from the original 14.59 MPa to the maximum 24.18 MPa at 1.5 phr of SiO₂@PS-PMMA JPs, and the elongation at break increased from 39% to 203%.     

Microstructure control of highly oriented short carbon fibres in SiC matrix composites fabricated by direct ink writing

A novel method is proposed for fabricating highly oriented carbon fibre reinforced SiC ceramic composites (C_f/SiC) by direct ink writing (DIW). For the first time, the control of carbon fibers’ orientation in DIW was studied by numerical simulation. An interfacial layer was prepared by chemical vapor infiltration (CVI). The microstructure and phase composition of C_f/SiC were studied by scanning electron microscopy and X-ray diffraction, respectively. The results showed that fibers of different interfacial thicknesses could be obtained effectively by varying the CVI time. The breakage of short fibres remarkably improved the fracture toughness of the parts. The specimens showed excellent mechanical properties with bending strength of 274 ± 13 MPa and fracture toughness of 5.82 ± 0.25 MPa m^1/2. This method could be extended to the preparation of other resin and ceramic composites.     

Thermal properties and miscibility of semi‐crystalline and amorphous PLA blends

The focus of this research is the study of the microstructures and miscibility at the interface between semi‐crystalline and amorphous PLAs [poly (l ‐lactic acid)(PLLA) with poly (l ,d ‐lactic acid)(PDLLA), respectively]. The blends are prepared through thermal processing (extrusion and hot‐pressing). To increase the area of interface between PDLLA and PLLA, the fibers from PLLA and PDLLA are used. Thermal and microstructures of the blends were studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), dynamic thermogravimetric analysis(DMA), small‐angle X‐ray diffraction(SAXS) and wide‐angle X‐ray diffraction (WAXD). The two PLAs are miscible in molten state. However, phase separation is detected after various thermal treatments, with PDLLA being excluded from the regions of interlamellar PLLA regions when PDLLA content is low, as determined from X‐ray diffraction studies. The compatibility between the two PLAs is not perfect in the molten state, since enthalpies of the various blends at T_g are lower than any pure PLA material. The semi‐crystalline PLLA fiber can recrystallize alone in the molten amorphous PDLLA, and a higher nuclei density is observed at the interface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41205.     

Effect of preform and carbon matrix on bending strength of Cf/Cu/C composites

Aiming to obtain composites with appropriate mechanical properties for pantograph sliders, copper mesh modified carbon/carbon (C_f/Cu/C) composites were prepared by chemical vapor infiltration (CVI) in C₃H₆ +?N₂ atmosphere and impregnation-carbonization (I-C) with furan resin. In this paper, C_f/Cu/C composites with two kinds of preforms and carbon matrixes were obtained. The effect of preforms and carbon matrixes on bending strength was investigated. The results indicated that the bending strength of carbon fiber/copper mesh reinforced pyrolytic carbon matrix composites was about 181.39–195.43?MPa, while that reinforced resin carbon matrix composites had the worst bending strength around 54.45–57.04?MPa, in terms of the same preform. The bending strength of C_f/Cu/C composites in the parallel orientation and vertical orientation were also similar. As for C_f/Cu/C composites with the same carbon matrix, the bending strength of C_f/Cu/C composites with non-woven fiber/fiber web/copper mesh type preform was higher than that with fiber web/copper mesh type preform. However, the bending strength of carbon fiber/copper mesh reinforced resin carbon matrix composites showed the opposite trend, and its reasons were analyzed and discussed taking advantage of the fracture mechanisms.     

Development and evaluation of Al2O3–ZrO2 composite processed by digital light 3D printing

Digital Light Processing (DLP) is a promising approach to fabricate delicate ceramic components with high-fidelity structural features. In this work, the alumina and zirconia/alumina ceramic suspensions with low viscosity and high solid loading (40 vol%) were prepared specifically for DLP 3D printing. After debinding and sintering, the final parts were obtained without any defects. The surface morphologies and mechanical properties of alumina (Al₂O₃) and zirconia toughened alumina (ZTA) composites were investigated and the results showed that the final parts exhibited high relative densities and good interlayer combination at the sintering temperature of 1600 °C. Comparing with the Al₂O₃, the ZTA composites exhibited significantly enhanced density (99.4%), bending strength (516.7 MPa) and indentation fracture toughness (7.76 MPa m^1/2).     

Phase structure and properties of poly(ethylene terephthalate)/high‐density polyethylene based on recycled materials

Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χ_c) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (T_c) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χ_c of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel Layered Hydroxyapatite/Tri‐Calcium Phosphate–Zirconia Scaffold Composite with High Bending Strength for Load‐Bearing Bone Implant Application

The integration of biological and mechanical requirements remains a challenge in developing porous hydroxyapatite (HA) and tri‐calcium phosphate (TCP) scaffolds for load‐bearing bone implant application. With the newly developed slip‐deposition and coating‐substrate co‐sintering technique, a strong layered HA/TCP‐zirconia scaffold composite structure was successfully fabricated. The bending strength (321 MPa) of this composite can match upper strength limit of the natural compact bone. The HA‐based scaffold coating has multiple scale porous structures with pore size ranging 1–10 and 20–50 μm. The zirconia‐based substrate is also porous with submicropores. Focus ion beam micrographs show most of the micropores in the coating are interconnected. Microindentation and primarily adhesive strength tests demonstrate that the scaffold coating strongly bonds with the zirconia based substrate. In vitro cell culture study indicates that the coatings have no cytotoxicity. It is evident that the strong layered HA–zirconia scaffold composite offers new implant options for bone repairs requiring immediate load bearing capacity.     

PET/PC blends: Effect of chain extender and impact strength modifier on their structure and properties

Methylene diphenyl diisocyanate (MDI) affects the morphology, rheological, mechanical, and relaxation properties, as well as tendency to crystallize of PET in PET/PC/(PP/EPDM) ternary blends produced by the reactive extrusion. Irrespective of the blend phase structure, the introduction of MDI increases the melt viscosity (MFI dropped), resulting from an increase in the molecular weight of the polymer chains; the PET crystallinity was also reduced. MDI favors compatibility of PET with PC in PET/PC/(PP/EPDM) blends. This is explained by intensified interphase interactions on the level of segments of macromolecules as well as monomer units. The presence of MDI causes a substantial rise in the dynamic shear modulus within the high‐elastic region of PET (for temperature range between T_g,PET and that of PET cold crystallization); the processes of PET cold crystallization and melt crystallization become retarded; the glass‐transition temperatures for PET and PC become closer to each other. MDI affects insignificantly the blend morphology or the character of interactions between the disperse PP/EPDM blend and PET/PC as a matrix. PP/EPDM reduces the intensity of interphase interactions in a PET/PC/(PP/EPDM), but a rise in the degree of material heterogeneity. MDI does not change the mechanism of impact break‐down in the ternary blends mentioned above. Increased impact strength of MDI‐modified materials can be explained by higher cohesive strength and resistance to shear flow at impact loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011