多孔生物陶瓷与PVA水凝胶复合材料的制备与力学性能分析

目的将多孔生物陶瓷和聚乙烯醇(PVA)水凝胶交联成为一个仿生软骨-硬关节双层结构,并对该结构的微观形貌和力学性能进行分析。方法以羟基磷灰石(HA)为基体,采用添加碳酸氢铵(NH4HCO3)晶粒造孔的方式制备不同孔隙率的多孔羟基磷灰石生物陶瓷,以聚乙烯醇(PVA)为主要原料,环氧丙烷为交联剂,在多孔生物陶瓷表面及基体内交联制备出PVA水凝胶形成双层结构,对试样的断口形貌进行表征,对试样的拉伸强度和剪切强度等性能进行测试分析。结果交联的PVA水凝胶可以渗入到生物陶瓷基体表层以下的孔隙中,并且陶瓷基体和PVA水凝胶有很好的结合。随着多孔生物陶瓷孔隙率的增大,试样的最大拉伸和剪切负载均增大,平均孔隙率为70%试样的最大拉伸和剪切负载分别为153.61 N和64.46 N;而相应的拉伸和剪切强度略有下降,平均孔隙率为30%试样对应的最大拉伸和剪切强度分别为2.12 MPa和1.13 MPa。两者的失效形式均是因为裂纹的扩展,断口的微观形貌表明,断裂面存在明显的裂纹和内部缺陷,同时可观察出裂纹源和扩展方向。结论考虑到多孔生物陶瓷基体的强度,平均孔隙率为50%的多孔生物陶瓷的渗入效果适中,试样的拉伸强度和剪切强度、多孔生物陶瓷基体的压缩强度也有一定的保证,选择孔隙率为50%的试样较为合适。     

Mechanical and biological properties of apatite composite resins

Well-crystallized hydroxyapatite was synthesized at 80 degrees C and pH 7.4, and mixed as filler with 2.2'(4-methacryloxydiethoxyphenyl) propane. BPO and DHPT were used as polymerization initiators. The compressive strength and Knoop hardness of the apatite composite resins increased with the increase of apatite content, and approached a plateau above an apatite-resin ratio (Ap/R) of 1. The thermal expansion coefficient of the composite with apatite-resin ratio Ap/R = 1 was almost equal to that of teeth. In tooth cavities, the composites seemed to adhere well to enamel without a bonding agent. The biocompatibility of the composites implanted hypodermically into rats appeared to improve with the increase of apatite content, and implants showed no significant inflammation after 1 wk and 4 wk.     

Multi-scale hierarchy of Chelydra serpentina: microstructure and mechanical properties of turtle shell

Carapace, the protective shell of a freshwater snapping turtle, Chelydra serpentina, shields them from ferocious attacks of their predators while maintaining light-weight and agility for a swim. The microstructure and mechanical properties of the turtle shell are very appealing to materials scientists and engineers for bio-mimicking, to obtain a multi-functional surface. In this study, we have elucidated the complex microstructure of a dry Chelydra serpentina’s shell which is very similar to a multi-layered composite structure. The microstructure of a turtle shell’s carapace elicits a sandwich structure of waxy top surface with a harder sub-surface layer serving as a shielding structure, followed by a lamellar carbonaceous layer serving as shock absorber, and the inner porous matrix serves as a load-bearing scaffold while acting as reservoir of retaining water and nutrients. The mechanical properties (elastic modulus and hardness) of various layers obtained via nanoindentation corroborate well with the functionality of each layer. Elastic modulus ranged between 0.47 and 22.15 GPa whereas hardness varied between 53.7 and 522.2 MPa depending on the microstructure of the carapace layer. Consequently, the modulus of each layer was represented into object oriented finite element (OOF2) modeling towards extracting the overall effective modulus of elasticity (∼4.75 GPa) of a turtle’s carapace. Stress distribution of complex layered structure was elicited with an applied strain of 1% in order to understand the load sharing of various composite layers in the turtle’s carapace.     

Structure and mechanical properties of Saxidomus purpuratus biological shells

The strength and fracture behavior of Saxidomus purpuratus shells were investigated and correlated with the structure. The shells show a crossed lamellar structure in the inner and middle layers and a fibrous/blocky and porous structure composed of nanoscaled particulates (∼100 nm diameter) in the outer layer. It was found that the flexure strength and fracture mode are a function of lamellar organization and orientation. The crossed lamellar structure of this shell is composed of domains of parallel lamellae with approximate thickness of 200–600 nm. These domains have approximate lateral dimensions of 10–70 μm with a minimum of two orientations of lamellae in the inner and middle layers. Neighboring domains are oriented at specific angles and thus the structure forms a crossed lamellar pattern. The microhardness across the thickness was lower in the outer layer because of the porosity and the absence of lamellae. The tensile (from flexure tests) and compressive strengths were analyzed by means of Weibull statistics. The mean tensile (flexure) strength at probability of 50%, 80–105 MPa, is on the same order as the compressive strength (∼50–150 MPa) and the Weibull moduli vary from 3.0 to 7.6. These values are significantly lower than abalone nacre, in spite of having the same aragonite structure. The lower strength can be attributed to a smaller fraction of the organic interlayer. The fracture path in the specimens is dominated by the orientation of the domains and proceeds preferentially along lamella boundaries. It also correlates with the color changes in the cross section of the shell. The cracks tend to undergo a considerable change in orientation when the color changes abruptly. The distributions of strengths, cracking paths, and fracture surfaces indicate that the mechanical properties of the shell are anisotropic with a hierarchical nature.     

Multiscale aspects of mechanical properties of biological materials

Multiscale aspects of mechanical properties of biological materials have developed into an emerging area of research with impact in a broad range of disciplines ranging from medicine to materials science, defining a biomateriomics approach that facilitates a new paradigm in understanding the interplay of structure and function. Mechanical properties of biological materials are critical for virtually all physiological processes and cover all the scales, from the molecular to the macroscale, and provide access to mechanistic understanding and engineering design of novel tools for disease diagnosis, disease treatment and biomaterials development or for the transfer of biologically inspired materials and structures. The integrated use of simulation and experiment can address key challenges in this field and will result in new tools for the analysis and synthesis of complex materials.     

Effect of biphasic calcium phosphates on drug release and biological and mechanical properties of poly(epsilon-caprolactone) composite membranes

Poly(epsilon-caprolactone) (PCL) and biphasic calcium phosphate (CaP) composite membranes were prepared for use in tissue regeneration by a novel solvent casting-pressing method. An antibiotic drug, tetracycline hydrochloride (TCH), was entrapped within the membranes to investigate the efficacy of the material as a drug delivery system. The CaP powders were varied in amount (0-50 wt %) and in powder characteristics by heat treating at different temperatures, and their effects on the mechanical and biological properties and drug release of the membranes were examined. With CaP addition up to 30 wt %, the elastic modulus of the membranes was enhanced much due to the rigidity of CaP. While the tensile strength and elongation rate decreased gradually with CaP addition because the CaP powders acted as a failure source. The osteoblast-like cells cultured on the CaP-PCL composite membranes exhibited significant improvements in proliferation and alkaline phosphatase (ALP) activity compared to pure PCL and culture plastic control, indicating excellent cell viability and functional activity. The TCH drugs were released from the PCL and CaP-PCL membranes in a similar fashion; an initial burst followed by a reduced release rate. The initial burst effect diminished much by the addition of CaP powders. The CaP addition increased the drug release rate after an initial period, and this was attributed to the high water uptake capacity and dissolution of the CaP containing membranes. Compared to the composite membranes containing heat-treated CaP powders, those with as-precipitated ones had higher dissolution and drug releases. These observations on mechanical properties and cellular responses as well as on drug release profiles suggested that the CaP-PCL composite membranes are potentially applicable to tissue regeneration and drug delivery system.     

Effects of bioactive glass nanoparticles on the mechanical and biological behavior of composite coated scaffolds

Biphasic calcium phosphates (BCP) scaffolds are widely used for bone tissue regeneration. However, brittleness, low mechanical properties and compromised bioactivities are, at present, their major disadvantages. In this study we coated the struts of a BCP scaffold with a nanocomposite layer consisting of bioactive glass nanoparticles (nBG) and polycaprolactone (PCL) (BCP/PCL-nBG) to enhance its mechanical and biological behavior. The effect of various nBG concentrations (1-90 wt.%) on the mechanical properties and in vitro behavior of the scaffolds was comprehensively examined and compared with that for a BCP scaffold coated with PCL and hydroxyapatite nanoparticles (nHA) (BCP/PCL-nHA) and a BCP scaffold coated with only a PCL layer (BCP/PCL). Introduction of 1-90 wt.% nBG resulted in scaffolds with compressive strengths in the range 0.2-1.45 MPa and moduli in the range 19.3-49.4 MPa. This trend was also observed for BCP/PCL-nHA scaffolds, however, nBG induced even better bioactivity and a faster degradation rate. The maximum compressive strength (increased ～14 times) and modulus (increased ～3 times) were achieved when 30 wt.% nBG was added, compared with BCP scaffolds. Moreover, BCP/PCL-nBG scaffolds induced the differentiation of primary human bone-derived cells (HOBs), with significant up-regulation of osteogenic gene expression for Runx2, osteopontin and bone sialoprotein, compared with the other groups.     

Superior in vitro biological response and mechanical properties of an implantable nanostructured biomaterial: Nanohydroxyapatite–silicone rubber composite

A potential approach to achieving the objective of favorably modulating the biological response of implantable biopolymers combined with good mechanical properties is to consider compounding the biopolymer with a bioactive nanocrystalline ceramic biomimetic material with high surface area. The processing of silicone rubber (SR)–nanohydroxyapatite (nHA) composite involved uniform dispersion of nHA via shear mixing and ultrasonication, followed by compounding at sub-ambient temperature, and high-pressure solidification when the final curing reaction occurs. The high-pressure solidification approach enabled the elastomer to retain the high elongation of SR even in the presence of the reinforcement material, nHA. The biological response of the nanostructured composite in terms of initial cell attachment, cell viability and proliferation was consistently greater on SR–5 wt.% nHA composite surface compared to pure SR. Furthermore, in the nanocomposite, cell spreading, morphology and density were distinctly different from that of pure SR. Pre-osteoblasts grown on SR–nHA were well spread, flat, large in size with a rough cell surface, and appeared as a group. In contrast, these features were less pronounced in SR (e.g. smooth cell surface, not well spread). Interestingly, an immunofluorescence study illustrated distinct fibronectin expression level, and stronger vinculin focal adhesion contacts associated with abundant actin stress fibers in pre-osteoblasts grown on the nanocomposite compared to SR, implying enhanced cell–substrate interaction. This finding was consistent with the total protein content and SDS–PAGE analysis. The study leads us to believe that further increase in nHA content in the SR matrix beyond 5 wt.% will encourage even greater cellular response. The integration of cellular and molecular biology with materials science and engineering described herein provides a direction for the development of a new generation of nanostructured materials.     

Paclitaxel-eluting composite fibers: drug release and tensile mechanical properties

New core/shell fiber structures loaded with paclitaxel were developed and studied. These composite fibers are ideal for forming thin, delicate, biomedically important structures for various applications. Possible applications include fiber-based endovascular stents that mechanically support blood vessels while delivering drugs for preventing restenosis directly to the blood vesel wall, or drug delivery systems for treatment of cancer. The core/shell fiber structures were formed by "coating" dense core fibers with porous paclitaxel-containing poly(DL-lactic-co-glycolic acid) (PDLGA) structures. Shell preparation ("coating") was performed by freeze-drying water in oil emulsions. The present study focused on the effects of the emulsion's formulation (composition) and processing conditions on the paclitaxel release profile and on the fibers' tensile mechanical properties. In general, the porous PDLGA shell released approximately 40% of the paclitaxel, with most of the release occurring during the first 30 days. The main release mechanism during the tested period is diffusion, rather than polymer degradation. The release rate and quantity increased with increased drug content or decreased polymer content, whereas the organic:aqueous phase ratio had practically no effect on the release profile. These new composite fibers are strong and flexible enough to be used as basic elements for stents. We demonstrated that proper selection of processing conditions based on kinetic and thermodynamic considerations can yield polymer/drug systems with the desired drug release behavior and good mechanical properties.     

Retention of mechanical properties and cytocompatibility of a phosphate-based glass fiber/polylactic acid composite

Polymers prepared from polylactic acid (PLA) have found a multitude of uses as medical devices. The main advantage of having a material that degrades is so that an implant would not necessitate a second surgical event for removal. In addition, the biodegradation may offer other advantages. In this study, fibers produced from a quaternary phosphate-based glass (PBG) in the system 50P(2)O(5)-40CaO-5Na(2)O-5Fe(2)O(3) (nontreated and heat-treated) were used to reinforce the biodegradable polymer, PLA. Fiber properties were investigated, along with the mechanical and degradation properties and cytocompatibility of the composites produced. Retention of mechanical properties overtime was also evaluated. The mean fiber strength for the phosphate glass fibers was 456 MPa with a modulus value of 51.5 GPa. Weibull analysis revealed a shape and scale parameter value of 3.37 and 508, respectively. The flexural strength of the composites matched that for cortical bone; however, the modulus values were lower than those required for cortical bone. After 6 weeks of degradation in deionized water, 50% of the strength values obtained was maintained. The composite degradation properties revealed a 14% mass loss for the nontreated and a 10% mass loss for the heat-treated fiber composites. It was also seen that by heat-treating the fibers, chemical and physical degradation occurred much slower. The pH profiles also revealed that nontreated fibers degraded quicker, thus correlating well with the degradation profiles. The in vitro cell culture experiments revealed both PLA (alone) and the heat-treated fiber composites maintained higher cell viability as compared to the nontreated fiber composites. This was attributed to the slower degradation release profiles of the heat-treated composites as compared to the nontreated fiber composites. SEM analyses revealed a porous structure after degradation, and it is clear that there are possibilities here to tailor the distribution of porosity within polymer matrices.     

Water as a major modulator of the mechanical properties of insect cuticle

The mechanical properties of the sternal cuticle of the locust were investigated by nanoindentation. Modulus and hardness of the exo-, meso-, and endocuticular layers were locally measured under dry and fully wetted conditions in the normal (i.e. perpendicular to the outer surface) as well as in the transverse direction (i.e. parallel to the alignment of the respective layers). The results show that water has a major impact on the mechanical properties of all layers. After drying the endocuticle, in particular, became harder by a factor of up to 9 and stiffer by a factor of up to 7.4. Additionally the gradual decrease in hardness and Young's modulus from the outer exo- to the inner endocuticle, characteristic of native cuticle, was eliminated or even reversed in dried cuticle. A pronounced anisotropy was revealed in all layers when comparing data obtained by probing in the normal (lower values) vs. probing in the transverse direction (higher values). Cyclic drying and rewetting of the endocuticle showed that the mechanical properties can be reproducibly changed by altering the water content. Based on our results we propose a new role of the epicuticle: fine-tuning of the mechanical properties of the different cuticular layers can be accomplished by setting the local cuticular transpiration.     

Microwave-processed nanocrystalline hydroxyapatite: Simultaneous enhancement of mechanical and biological properties

Despite the excellent bioactivity of hydroxyapatite (HA) ceramics, poor mechanical strength has limited the applications of these materials primarily to coatings and other non-load-bearing areas as bone grafts. Using synthesized HA nanopowder, dense compacts with grain sizes in the nanometer to micrometer range were processed via microwave sintering between 1000 and 1150 °C for 20 min. Here we demonstrate that the mechanical properties, such as compressive strength, hardness and indentation fracture toughness, of HA compacts increased with a decrease in grain size. HA with 168 ± 86 nm grain size showed the highest compressive strength of 395 ± 42 MPa, hardness of 8.4 ± 0.4 GPa and indentation fracture toughness of 1.9 ± 0.2 MPa m^1/2. To study the in vitro biological properties, HA compacts with grain size between 168 nm and 1.16 μm were assessed for in vitro bone cell–material interactions with human osteoblast cell line. Vinculin protein expression for cell attachment and bone cell proliferation using MTT assay showed that surfaces with finer grains provided better bone cell–material interactions than coarse-grained samples. Our results indicate simultaneous improvements in mechanical and biological properties in microwave sintered HA compacts with nanoscale grain size.     

复合纳米人工骨的注射、凝固及其机械性能研究

目的 构建半水硫酸钙和纳米羟基磷灰石为主的复合人工骨材料并对其注射性能、凝固性能和机械强度的影响因素进行考察.方法 测试不同液固比条件下复合材料的注射特性,25℃和37℃时分别测试不同液固比、不同二水硫酸钙促凝剂条件下的材料初、终凝时间和压缩强度,均与纯硫酸钙作对比.结果 液固比0.50以上时注射性能满意.无论何种液/固比,复合材料的凝固时间均较硫酸钙延长,37℃下的凝固时间较25℃下延长.一定范围内促凝剂用量过大或过小均使凝固时间延长.液固比越大或促凝剂用量越高,材料压缩强度越低.纳米磷灰石含量增大则材料强度降低.结论 合理掌握纳米磷灰石的比例,液固比和促凝剂的用量,是开发可注射纳米人工骨的关键.     

Application of the composite model for the mechanical properties of high density polyethylene

The existing models of high density polyethylene (HDPE) fail to tackle effectively the development of mechanical anisotropy on drawing at different temperatures. This paper is concerned with the theoretical interpretation of the anisotropic elastic properties of HDPE by applying the composite model proposed by the authors. The model takes into account the change in orientation and crystallinity on drawing. As far as the orientational changes on drawing are concerned, it is seen that the pseudo affine deformation law tan θ = ?(n) · tan θ′ with ?(n) = n^?3/2 is applicable at ?60°C only. It is further found that the two parameter analytical form of ?(n) reproduces the correct orientational changes on drawing for the entire temperature range from ?60 to 100°C. The agreement of the calculated values of E₀ and E₉₀ over the entire temperature range at all drawing ratios is quite satisfactory.     

Effect of temperature and ageing on the mechanical properties of dental polymeric composite materials

Evaluation of the mechanical properties of some dental composite materials, Compact, Finesse and Prisma-Fil based on bisphenol glycidyl methacrylate resin was undertaken by applying compression, tension and hardness tests. The effects of temperature and ageing times on these properties were studied. There was a marked increase in the mechanical properties (compressive strength, diametral tensile strength, compressive elastic modulus and hardness) for all the investigated composites with increase of both temperature and time. This was explained in terms of the influence of temperature on the polymerization rate of the materials. The improvement in the mechanical properties of the samples, kept at 37 degrees C, was attributed to further and continued polymerization of the polymer content of their resin system. Such mechanical improvement was verified by the regression equation of linearity versus both temperature and time.     

Effects of postcuring and water sorption on the mechanical properties of composite dental restorative materials

Four commercial dental restorative composites with different filler contents, were tested for the effects of postcuring and water sorption on elastic modulus, compressive strength and ultimate strain. Large variations in mechanical properties were seen; water sorption plasticizes the matrix, causing loss of low molecular weight substances.