HA/HDPE多尺度生物复合材料的制备与力学性能

采用原位矿化复合-固相挤出技术制备羟基磷灰石/高密度聚乙烯(HA/HDPE)复合材料。结果表明,原位矿化-固相挤出制备的HA/HDPE复合材料是一种纳米HA颗粒均匀分散、界面结合强度高、HA/HDPE复合纤维定向排列的多尺度结构复合材料,在纳米尺度上HA均匀分散在HDPE基体中,在微米尺度上形成HA/HDPE复合纤维,在显微尺度上定向排列的HA/HDPE复合纤维形成织构结构。该HA/HDPE多尺度结构复合材料的力学性能与传统的熔融挤出的HA/HDPE复合材料相比有显著提高,拉伸强度达到245MPa,弯曲强度达到165MPa,拉伸模量为18.1GPa,力学性能均达到人体皮质骨的力学要求。     

羟基磷灰石/淀粉基复合生物材料

淀粉基(starch-based)材料是一类重要的生物降解聚合物,羟基磷灰石(HA)是人体骨骼的主要成分,以淀粉基材料为基体、以HA为增强材料的HA/淀粉基复合材料是一类新型的复合生物材料,其具有良好的生物相容性,在骨修复领域具有巨大的应用潜力.初步对该复合材料进行了归类,并介绍了其制备工艺、性能和应用等方面的研究近况,指出改进复合工艺、采用纳米级HA增强并进行表面改性是其发展趋势.     

孔结构渐变聚己内酯/羟基磷灰石仿生骨材料

为获得具有类似人骨的渐变孔结构、力学性能良好的羟基磷灰石(hydroxyapatite,HA)/聚己内酯(polycaprolactone,PCL)仿生骨材料,采用水热法制备了HA粉末,通过溶剂共混法将其与PCL复合,并采用浇铸/NaCl微粒浸出法制备了多孔状HA/PCL复合材料.通过控制造孔剂NaCl的粒径和用量得到了不同孔径、不同孔隙率的HA/PCL复合材料及具有渐变孔结构的HA/PCL复合材料.利用光学显微镜观察了其孔结构,结果为孔径在100～300μm,最大孔隙率达到80%.同时研究了它们在人体体温附近(37±5)℃的力学性能,结果表明渐变孔结构的HA/PCL复合材料的力学性能较单一孔结构的HA/PCL复合材料有了很大的提高.通过梯度造孔不仅可获得与人骨极为类似的多孔仿生材料,同时还可大幅提高多孔材料的力学性能.     

羟基磷灰石/液晶复合材料仿生人工骨的制备及性能

通过优化的加工条件制备了羟基磷灰石/热致液晶高分子(HA/Vectra A950)复合材料仿生人工骨, 研究了HA含量对复合材料显微结构和力学性能的影响, 分析了HA与Vectra A950共混后的力学性能以及界面结合问题。研究结果表明: 当HA与Vectra A950的质量比小于10∶100时, 复合材料呈现明显的皮芯结构, 皮层液晶微纤高度取向, HA主要分散在芯部, 其模量和强度达到或超过天然骨的力学性能; 随着HA含量的增加, 皮芯结构逐步减弱并消失, 而缺陷显著增加。当HA与Vectra A950的质量比增加到20∶100, 复合材料的力学性能、尤其是韧性显著降低, 这可能是由于HA颗粒与液晶基体之间的结合较差导致的。为保证复合材料仿生人工骨的生物活性, HA的含量应与天然骨接近。因此, 需对HA和Vectra A950的界面进行改性以提高其结合性能。      

无机填料对木粉/高密度聚乙烯复合材料性能的影响

目的考察无机填料的种类、粒径以及添加量对PF/HDPE复合材料力学性能和热稳定性的影响。方法以杨木纤维(PF)、高密度聚乙烯(HDPE)、BaSO4、CaCO3、云母粉为原料,采用熔融共混和注塑成型的方法制备PF/HDPE复合材料,进行力学、热重、扫描电镜测试分析。结果3种无机填料均改善了PF/HDPE复合材料力学及热稳定性能,填充CaCO3获得的复合材料性能优于填充BaSO4、云母粉获得的复合材料,并且随着填料颗粒粒径的减少,改善效果增强。填料的添加量需要保持在一定范围内,添加量过低或过高均会造成性能下降。结论添加CaCO3(质量分数为9%,3000目)制备的PF/HDPE复合材料具有最佳的力学及热稳定性。     

抗氧化剂对硫酸钙晶须/高密度聚乙烯复合材料性能的影响

高密度聚乙烯（HDPE）存在耐热老化性、耐候性不足和易变性等缺陷,为此通过共混挤出制备了偶联剂改性硫酸钙晶须（CSW）/HDPE复合材料,并添加抗氧化剂1010作用于力学性能较优异的复合体系。通过扫描电镜观察到添加1010可减少复合体系的表面裂纹;力学性能测试表明,抗氧化剂1010对复合体系的力学性能具有抗老化效果,氧化时间为40 d时,抗老化效果更佳,保有率差最高为6.41%;通过热失重分析和差示扫描量热分析研究复合体系的热性能和结晶性能,证实抗氧剂1010可有效抑制热氧老化对偶联剂改性CSW/HDPE复合材料的损耗程度,阻止复合体系前期的热降解,使热性能更稳定,并提高了复合体系的结晶度。     

剪切增稠胶/超高分子量聚乙烯复合材料低速冲击性能研究

剪切增稠胶(STG)是一种新型功能材料,通过流变测试研究了STG的稳态流变性能及其剪切增稠的作用方式。将STG与超高分子量聚乙烯(UHMWPE)织物复合制备了STG/UHMWPE复合材料,利用扫描电子显微镜对复合前后材料的形貌进行分析,并研究了复合材料的低速冲击性能。结果表明:加入STG后,STG/UHMWPE复合材料的剩余冲击载荷可减少50%;在不同冲击速度条件下,复合材料能量吸收系数均超过80%。STG具有优异的力学性能,通过与UHMWPE织物复合可显著提高复合材料的抗冲击性能。     

聚乳酸/聚乙二醇/羟基磷灰石多孔骨支架的3D打印制备及其生物相容性

聚乳酸(PLA)是一种应用广泛的生物高分子材料,但在应用过程中存在韧性、亲水性、生物活性差等缺点。用聚乙二醇(PEG)和羟基磷灰石(HA)对PLA进行改性。通过熔融共混制备不同质量比的PLA/PEG/HA复合3D打印线材,并通过分析PLA/PEG/HA线材的力学性能、结晶性能、热性能、流变性能等,筛选更适合熔融沉积成型(FDM)的3D打印成型线材,进而利用3D打印制备精度高的力学性能试样及生物相容性好、细胞可增殖和分化的生物多孔支架。结果表明:PEG的添加提高了PLA的韧性,降低了PLA的熔点。HA的添加则提高PLA/PEG/HA复合材料的弹性模量和冷结晶温度,同时HA也可以改善复合材料的加工性能。SEM与荧光标记结果表明多孔支架与细胞具有良好的生物相容性。生物支架对体外细胞的成功培养,为进一步发掘生物多孔支架在动物体内、生物医学及定制化应用方面提供了潜在可能。     

羟基磷灰石的表面改性对羟基磷灰石/聚醚醚酮复合材料力学和摩擦性能的影响

采用共沉淀法制备纳米羟基磷灰石（HA）,并用硅烷偶联剂KH560对其进行表面改性;然后,以聚醚醚酮（PEEK）为基体,通过热压成型工艺制备原始HA/PEEK与改性HA/PEEK复合材料。考察两种HA的引入对复合材料结构、力学性能和摩擦性能的影响。利用XRD、FTIR、FESEM、拉伸测试、DMA和摩擦测试对两种HA/PEEK复合材料的结构和性能进行了表征。结果表明：HA表面引入了硅烷偶联剂KH560;改性前后HA的晶型结构没有明显改变;两种HA对PEEK基体的结晶结构也没有产生影响;改性HA在PEEK基体中分散均匀;与纯PEEK相比,10wt%改性HA/PEEK复合材料的储能模量增加了55.56%,玻璃化温度增加了3.6℃,磨痕深度降低了31.1%,有效改善了复合材料的热力学性能和摩擦性能;改性HA/PEEK拉伸强度为68.33 MPa,能够满足人骨的强度要求。     

改性石墨烯/高密度聚乙烯复合材料PTC性能研究

以高密度聚乙烯(HDPE)为基体,改性的石墨烯为导电填料,采用熔融法制备正温度系数(PTC)的改性石墨烯/高密度聚乙烯复合材料。通过扫描电子显微镜、热重测试仪以及拉伸测试仪等,观察改性石墨烯/高密度聚乙烯复合材的微观形貌,研究改性石墨烯含量对复合材料热稳定性的影响以及拉伸性能的影响。结果表明:石墨烯在HDPE基体中分散性较好,在室温电阻率同为18.5Ω·㎝条件下,改性前复合材料耐电压冲击为250V,改性后复合材料耐电压冲击为400V,改性后的石墨烯加入HDPE,能够明显地提高复合材料增强耐电压性能,在石墨烯用量同为8.0%(体积百分数)条件下,改性前石墨烯的复合材料拉伸强度为25.6MPa,改性后石墨烯的复合材料拉伸强度为27.7MPa,改性后的石墨烯加入HDPE,能够明显提高复合材料的拉伸强度。     

Effect of low content reed (Phragmite australis) fibers on the mechanical properties of recycled HDPE composites

This paper discusses the influence of low content red fibers on the mechanical characteristics of recycled HDPE composites. Composites of High Density Polyethylene (HDPE) and common reed (Phragmite australis) natural fibers were prepared by successive single screw extrusion blending. The mechanical and thermal properties of these composites which have low concentrations of fibers were investigated. It was found that the number of extrusions had no effect on the thermal stability of composites, even if the presence of fibers may be accelerating the degradation of the polymer matrix. Moreover, rheological measurements showed a decrease in the viscosity of the neat matrix, while the opposite was observed in composites for which the highest viscosity is obtained after five cycles of extrusion. These results suggest a decrease in the molecular weight of the HDPE during reprocessing. For composites, however, a good dispersion of the RF matrix was obtained, which increased as the number of extrusions grew larger. As for the mechanical properties, a substantial enhancement in ductility was observed, as compared to that of neat recycled matrices, when small RF concentrations were added. Thus, for 2.6% RF the best enhancement of ductility was obtained with the conservation of the fiber length and a good dispersion of fibers. These findings show that incorporating low contents of reed fibers can be an interesting solution when trying to improve the mechanical behavior of recycled polyethylene.     

聚乙二醇改性相变微胶囊制备MicroPCMs-WF/HDPE复合材料物理力学性能

以正十二烷醇（DA）为芯材,密胺树脂（MF）和聚乙二醇改性密胺（PMF）树脂为壁材制备了相变微胶囊（MicroPCMs）,并分别添加到木粉/高密度聚乙烯（WF/HDPE）复合材料中,获得了具有相变蓄热能力的MicroPCMs-WF/HDPE复合材料。采用SEM、FTIR和纳米压痕等方法对MicroPCMs的表面形态、力学性能进行了分析与表征,同时对MicroPCMs-WF/HDPE复合材料的物理力学及热性能进行了测试。结果表明:经聚乙二醇改性后,改性微胶囊（PMF-MicroPCMs）的弹性模量和硬度较未改性微胶囊（MF-MicroPCMs）分别增加了13.9%和30.0%;MicroPCMs-WF/HDPE复合材料的熔融温度区间（22.2~28.7℃）满足人体舒适温度范围,较纯WF/HDPE复合材料温度变化速率明显减缓;相比纯WF/HDPE复合材料,MicroPCMs-WF/HDPE复合材料的吸湿性、冲击强度和表面硬度增加,弯曲和拉伸性能下降;PMF-MicroPCMs-WF/HDPE复合材料的性能均优于MF-MicroPCMs-WF/HDPE复合材料,且达到了木塑装饰板材的力学性能标准要求。      

短切碳纤维表面处理对木粉/高密度聚乙烯复合材料性能的影响

木粉（WF）填充增强高密度聚乙烯（HDPE）复合材料具有良好的环境效益,少量引入短切碳纤维（SCF）可进一步提高其力学性能。为改善SCF与WF/HDPE复合材料中塑料基体的界面结合,提高SCF在WF/HDPE复合材料中的增强作用,采用气相、液相及气液双效氧化3种表面处理方式处理SCF,通过挤出工艺制备短切碳纤维增强木粉/高密度聚乙烯复合材料（SCF-WF/HDPE）,探讨了不同处理方法对SCF-WF/HDPE复合材料性能的影响。SEM观察显示,表面处理增大了SCF的表面粗糙度,可提高其与基体的界面结合;动态力学性能分析证实碳纤维提高了存储模量。测试结果表明：表面处理过的短切碳纤维可使SCF-WF/HDPE复合材料的力学性能、热力学性能和蠕变性能均得到显著提高,其中气相表面处理的效果最好。对比WF/HDPE复合材料,SCF-WF/HDPE的拉伸强度提高了34.5%,弯曲强度提高了23%,冲击强度提高了54.7%。     

Processing and properties of bone-analogue biodegradable and bioinert polymeric composites

This paper summarizes the processing and properties of bone-analogue composites aimed to be used in temporary or permanent orthopaedic applications. The studied matrices were two biodegradable starch based blends (with ethylene-vinyl alcohol copolymer or with cellulose acetate) and three high density polyethylene (HDPE) grades. Composites of these materials with hydroxyapatite (HA—the main inorganic constituent of the human bone) were produced by extrusion compounding and subsequently injection moulded. A non-conventional injection moulding technique known as shear controlled orientation in injection moulding (SCORIM) was used deliberately to induce a strong anisotropic character to the processed composites. For the case of HDPE based composites, an alternative reinforcement system based on carbon fibres (C fibres) was also studied. For that, a special moulding technique that combines, in a single equipment, a compounding with an injection unit was used. Composites featuring a sandwich like structure were also produced by mono-sandwich injection moulding. These composites combine a HDPE/HA outer layer and HDPE/C fibre reinforced core. The aim is to produce composites with a mechanical behaviour matching that of human cortical bone and simultaneously a strong bioactive (bone-bonding) character. For all the cases, the mechanical performance of the produced composites was assessed and the structure developed investigated and related to the processing conditions. It was possible to produce, both biodegradable and bioinert matrix composites, with properties that might allow for their application in the orthopaedic field.     

铝矾土改性竹粉/HDPE复合材料性能

为制备高性能的木塑复合材料,扩展其应用领域,采用A-171硅烷偶联剂对竹粉进行表面改性,并添加一定量的铝矾土,经热压成型制备了竹粉/高密度聚乙烯(HDPE)复合材料。分析了铝矾土用量对竹粉/HDPE复合材料力学性能、耐热性和摩擦性能的影响。采用XRD分析了铝矾土的结晶特性,利用SEM和EDS分析了竹粉/HDPE复合材料的断面形貌和表面元素分布情况。结果表明:加入适量铝矾土后,竹粉/HDPE复合材料的力学强度、耐热性及耐磨性能得以改善。铝矾土在竹粉/HDPE复合材料基体中分布均匀,可有效承担载荷,同时提高了竹粉/HDPE复合材料的结晶性能,降低了竹粉/HDPE复合材料在外在应力下引起的变形和破坏;但铝矾土用量过高,分布不均匀,容易形成团聚现象,导致竹粉/HDPE复合材料的力学强度和耐磨性降低,线性热膨胀系数增大。     

Mechanical,thermal expansion,and flammability properties of co-extruded wood polymer composites with basalt fiber reinforced shells

Basalt fiber (BF) filled high density polyethylene (HDPE) and co-extruded wood plastic composites (WPCs) with BF/HDPE composite shell were successfully prepared and their mechanical, morphological and thermal properties characterized. The BFs had an average diameter of 7 μm with an organic surfactant surface coating, which was thermally decomposed at about 210 °C. Incorporating BFs into HDPE matrix substantially enhanced flexural, tensile and dynamic modulus without causing a noticeable decrease in the tensile and impact strength of the composites. Micromechanical modeling of tensile properties for the BF/HDPE composites showed a good fit of the selected models to the experimental data. Compared to neat HDPE, BF/HDPE composites had reduced linear coefficient of thermal expansion (LCTE) values. The use of the pure HDPE and BF/HDPE layers over a WPC core greatly improved impact strength of core–shell structured composites. However, the relatively less-stiff HDPE shell with large LCTE values decreased the overall composite modulus and thermal stability. Both flexural and thermal expansion properties were enhanced with BF reinforced HDPE shells, leading to well-balanced properties of core–shell structured material. Cone calorimetry analysis indicated that flammability performance of core–shell structured composites was improved as the BF content increased in the shell layer.     

Improved mechanical properties of HIPS/hydroxyapatite composites by surface modification of hydroxyapatite via in-situ polymerization of styrene

High impact polystyrene (HIPS)/hydroxyapatite (HA) composites are potential biomaterials for bone replacements due to their good biocompatibility and adequate mechanical properties. At the present work, the surface of the micron-sized hydroxyapatite (HA) particles was modified by in situ polymerization of styrene (St), then compounded with HIPS. The effect of the modification of HA surface on morphology and mechanical properties of HIPS/HA composites were investigated. The results showed that the HA particles does not inhibit the polymerization of St. The PS segments coated on the HA surface by in situ polymerization of St enhances the compatibility between HA and HIPS, improves the dispersion of HA particles in HIPS matrix, and enhances the interfacial adhesion between HA and matrix. Thereby, the stiffness, tensile strength and notch impact strength of HIPS/HA composites are improved at the same time. And there is a critical coating thickness of PS on the HA surface for the optimum mechanical properties of HIPS/HA composites.     

Thermal conductivity and mechanical properties of high density polyethylene composites filled with silicon carbide whiskers modified by cross-linked poly (vinyl alcohol)

A thin layer of poly (vinyl alcohol) (PVA) was coated on the surface of silicon carbide whiskers (SCWs) and crosslinked by glutaraldehyde, and then these modified whiskers (mSCWs) were incorporated into high density polyethylene (HDPE) to prepare HDPE/mSCW composites with a high thermal conductivity. The thermal conductivity, mechanical properties, heat resistance, thermal stability and morphology of HDPE/mSCW and HDPE/SCW composites were characterized and compared. The results reveal that the thermal conductivity of both HDPE/SCW and HDPE/mSCW composites increases with the increase of filler loading, and reaches a maximum of 1.48 and 1.69?W/(m?K) at 40?wt% filler loading, which is 251.2% and 300.75% higher than that of HDPE, respectively. Significantly, HDPE/mSCW composites have a higher thermal conductivity than their HDPE/SCW counterparts with the same filler loading. In addition, the heat resistance, Young’s modulus and yield strength of both HDPE/SCW and HDPE/mSCW composites are also improved compared with that of HDPE. mSCW can be homogenously dispersed in the HDPE matrix, which contributes to the formation of thermally conductive networks by the inter-connection of mSCWs.