天然橡胶/石墨烯纳米复合材料的制备及耐核辐射性能

采用乳液共混和原位还原法制备了天然橡胶(NR)/还原氧化石墨烯(RGO)纳米复合材料,研究了γ射线辐照对复合材料力学性能和热稳定性的影响.研究结果表明,RGO以少数几层堆叠片层结构均匀分散于NR基体中.RGO的加入可显著提高NR的力学性能和热稳定性,加入质量分数为0.6%的RGO可使材料拉伸强度由(22±1.4)MPa提升至(25±1.1)MPa,质量损失50%对应的温度(T50)升高6.4℃.经200 k Gy的γ射线辐射后,纯NR的拉伸强度和T50分别下降了75%和4.5℃,而NR/RGO-0.6%复合体系仅分别下降了56%和1.2℃.揭示了RGO提高材料耐辐射性能的机理,由于RGO可捕捉猝灭因辐射产生的自由基,从而减弱了辐射老化降解和交联反应的发生.     

纳米纤维素晶须的表面改性及其在环氧树脂中的应用

以棉纤维素为原料,采用硫酸水解法制备了纳米纤维素晶须.以N,N-二甲基甲酰胺(DMF)为分散介质,二甲基氨基吡啶(DMAP)为催化剂,十二烯基琥珀酸酐为酯化剂对纳米纤维素晶须进行化学改性,得到了一系列取代程度不同的改性产物(记为DCNW).采用红外光谱(FTIR)、X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对DCNW的结构和性能进行了分析和表征.选择表面取代度为0.3的改性产物作为复合材料的增强相.该改性产物能在丙酮中均匀分散和稳定悬浮,并且保持了改性前纳米纤维素晶须的棒状形态和高结晶度.将其分散于环氧单体中,通过浇铸法制备了纳米复合材料,考察了改性纳米纤维素晶须添加量对纳米复合材料拉伸性能、动态力学性能及耐湿热性的影响规律.结果表明,与空白环氧树脂相比,添加了改性纳米纤维素晶须的纳米复合材料的拉伸强度、杨氏模量和断裂伸长率都得到了提高.玻璃化转变温度、耐湿热性也得到了显著改善.其中,当改性纳米纤维素晶须的添加量为3.5%时,拉伸强度从纯环氧的39.85 MPa提高到72.33 MPa,增加了82%;杨氏模量增大了21%;断裂伸长率从纯环氧树脂的2.45%提高到7.29%,增加了198%;Tg值从纯环氧的103.4℃,提高到134.1℃;吸水率从1.9%下降到1.4%.     

累托石/聚丙烯插层纳米复合材料的制备与性能

采用熔融共混法制备了有机改性累托石 (OREC)粘土 均聚聚丙烯 (PP)纳米复合材料 ,以X 射线衍射分析 (XRD)及透射电子显微镜分析 (TEM)观察了复合材料的相貌结构 ,研究了复合材料的力学性能及热性能 .结果表明 ,OREC在添加份数较少时可与均聚聚丙烯熔融插层形成插层型聚丙烯纳米复合材料 ,该复合材料与纯PP相比 ,具有较高的拉伸强度、断裂伸长率及冲击强度 .在有机粘土添加 2 %时 ,复合材料的拉伸强度、断裂伸长率、冲击强度最高 ,与纯PP相比 ,2 %添加量的聚丙烯纳米复合材料拉伸强度提高 6 5 7% ,断裂伸长率提高 2 89 3% ,冲击强度提高 14 1% ,10 %失重率时对应的热分解温度提高 50K .     

纳米微晶纤维素对炭黑补强天然橡胶力学性能和动态性能的影响

采用酸水解工业微晶纤维素(MCC)制备纳米微晶纤维素(NCC),将其与天然胶乳共凝沉,混炼时加入炭黑(CB),制备了天然橡胶(NR)/NCC/CB复合材料,研究了NR/NCC/CB和NR/NCC/CB/RH(间苯二酚-六亚甲基四胺络合物)复合材料的力学性能和动态性能,并与NR/CB体系的性能进行对比.结果表明NCC可以均匀分散在天然橡胶基体中,且依拉伸方向取向,随着NCC替代炭黑的份数增加,Payne效应减弱,说明NCC本身并不构成强的填料网络,NR/NCC/CB与NR/CB比较,前者整体的网络化程度减弱,体系的损耗因子变化不大,NCC的加入改善了NR/CB的力学性能和抗屈挠龟裂性能,降低压缩疲劳温升和压缩永久形变,当NCC取代5～20 phr CB后,仍然保持高耐磨炭黑补强天然橡胶的耐磨耗性能.动态力学性能显示NR/NCC/CB的玻璃化转变温度较NR/CB变化不大,0℃的tanδ略有下降的同时60℃的tanδ明显降低.NR/NCC/CB/RH体系的Payne效应较NR/NCC/CB明显减弱,力学性能、抗屈挠龟裂性能和耐磨耗性能进一步改善,体系的压缩疲劳温升和压缩永久形变更小.     

基于天甲橡胶的高性能生物基弹性体制备及性能研究

天甲橡胶(MGNR)是生物基高分子材料天然橡胶(NR)的一种改性产品,较高的门尼黏度导致MGNR作为橡胶制品主要成分的研究鲜见报道.本文将极性的MGNR与非极性的NR并用,NR分子链较高的柔顺性使MGNR的门尼黏度得到有效降低,改善了MGNR的加工性能.进而添加表面具有硅羟基的气相法白炭黑,一方面,白炭黑与MGNR、NR形成结合胶;另一方面,白炭黑表面的硅羟基与MGNR的侧链甲基丙烯酸甲酯形成较强的相互作用,白炭黑作为"桥梁"改善了MGNR与NR之间的相容性.随着白炭黑含量的提高,MGNR/NR(40/60)硫化胶的拉伸强度与断裂伸长率均逐渐增大.当白炭黑的填充量为10 phr时,硫化胶的拉伸强度为31.2 MPa,断裂伸长率为605%.相比于未填充白炭黑的硫化胶分别提高了42.4%和28.9%,相比于纯MGNR分别提高了55.2%和93.9%.     

明胶中α组分含量对明胶/羟基磷灰石复合材料力学性能的影响

选用α组分含量分别为20.5%,41%和50%的A、B、C 3种明胶作为原料,采用同时加入法制备了明胶/羟基磷灰石(HAP)复合材料.通过对干态复合物膜拉伸性能的测试和对比,发现,明胶α组分含量的变化对复合材料的弹性模量影响较大,而对拉伸强度和断裂伸长率的影响则相对较小,但总的来说,三者均随α组分含量的增加而增大.其中,α组分含量最高的复合物C的拉伸强度为86.40 MPa,弹性模量为2682.35 MPa,断裂伸长率为8.65%.另外,对复合物C基本性质的表征结果表明,该材料具有类似于自然骨的组成和结构性质,因此有望成为一种具有优异力学性能的骨替代材料.     

壳聚糖/氧化石墨烯纳米复合材料的形态和力学性能研究

通过溶液共混法成功制备了氧化石墨烯/壳聚糖纳米复合材料. 透射电镜(TEM)结果表明, 氧化石墨烯纳米粒子在壳聚糖基体中分散良好. 拉伸实验结果表明, 随氧化石墨烯含量的增加, 氧化石墨烯/壳聚糖纳米复合材料的杨氏模量和拉伸强度均显著改善, 加入4 wt%的氧化石墨烯能够使纳米复合材料的杨氏模量和拉伸强度分别提高123%和117%|但另一方面, 却也在一定程度上使复合材料的断裂伸长率或韧性下降.     

聚乳酸纤维对热塑性淀粉塑料性能的影响

为增强热塑性淀粉(TPS)的力学及耐水性能,通过挤出注塑工艺制备了聚乳酸纤维(PLAF)增强的TPS复合材料(PLAF/TPS)。采用万能试验机、扫描电镜(SEM)、接触角测定仪、热重分析仪(TG)和转矩流变仪对PLAF/TPS复合材料的性能进行了表征。结果表明:适量的PLAF能够较好地分散在TPS基体中,并与淀粉分子形成氢键,从而显著增强TPS的力学及耐水性能。当PLAF的添加量(质量分数)为1.0%时,复合材料的拉伸强度及冲击强度从纯TPS的1.98 MPa、33.45kJ/m~2提高到6.79MPa、43.71kJ/m~2,断裂伸长率有所下降;PLAF的添加能使复合材料表面的接触角由纯TPS的46.3°增加到最大88.5°,耐水性能显著改善;PLAF使TPS的热稳定性略有提高;PLAF/TPS复合材料的加工性能随着PLAF添加量的增加而变差,当PLAF添加量为1.0%时,PLAF/TPS适宜加工成型。     

聚甲基乙撑碳酸酯/氧化石墨烯纳米复合材料的制备及性能研究

本文采用改进Hummers法制备氧化石墨烯(GO),通过原子力显微镜对GO片层形貌进行表征;以聚甲基乙撑碳酸酯(PPC)、聚乙烯醇(PVA)和氧化石墨烯(GO)为原料,采用溶液和熔融共混法相结合,制备PPC/PVA/GO纳米复合材料,研究其力学性能、热学性能和动态流变行为。结果表明,当GO含量为0.5 wt%时,拉伸强度达到了22.03 MPa,与纯PPC相比提高了25.8%;当GO含量增大到1.0 wt%时,拉伸强度开始降低;断裂伸长率随GO的加入呈现降低的趋势。GO含量为1.0%时复合材料的热学性能最好,与纯PPC相比,复合材料的完全热分解温度从350℃提高到了400℃以上,并且热分解速率下降了12%/min;复合材料的复数黏度、储能模量和损耗模量随PVA及GO的引入也有一定程度的提高。     

多官能度噁唑烷的合成及其改性聚氨酯材料

合成了2,2-二甲基-N-羟乙基-1,3-噁唑烷(OX),并以其为结构单元合成了2种多官能度的噁唑烷化合物——丙二酸二-2,2-二甲基-N-羟乙基-1,3-噁唑烷酯(OX1)和1,1,5,5-戊烷端四甲酸四-2,2-二甲基-N-羟乙基-1,3-噁唑烷酯(OX2).采用13C核磁共振谱、质谱、元素分析和傅里叶变换红外光谱对产物结构进行表征,并探索了产物用于单组份湿固化聚氨酯(SPU)体系的潜固化剂性能.研究了固化体系的表观性能、力学性能和热性能.结果表明:纯湿固化SPU发泡且膨胀,拉伸强度为3.2 MPa,断裂伸长率为364%;而SPU-OX2固化体系的拉伸强度达27.2 MPa,是纯SPU固化体系拉伸强度(3.2 MPa)的9倍;SPU-OX2固化体系断裂伸长率达457%,是纯SPU固化体系断裂伸长率(364%)的1.26倍.聚氨酯中加入噁唑烷OX1和OX2为潜固化剂,不仅较好改善了聚氨酯的表观性能,而且增加了聚氨酯预聚体的力学性能和热稳定性.     

Fabrication of Single Wall Carbon Nanotubes-Based Poly(vinyl butyral) Nanocomposites with Enhanced Mechanical and Thermal Properties

In this research, poly(vinyl butyral) (PVB)/single wall carbon nanotubes (SWCNT) composites were prepared via solution blending method. Dispersion degree of SWCNT in the composites was characterized by Scanning Electron Microscopy (SEM) and mechanical properties were measured with tensile testing. Thermal degradation of composites was investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). SEM analysis confirmed good dispersion of the nanotubes in the PVB. The tensile tests showed significant increases in mechanical properties such as exceptional improvement in tensile strength, Young's modulus and flexibility for the composites compared to PVB at low SWCNT content.The TGA curves indicated that adding SWCNT improved the thermal stability of the PVB significantly and the degradation of the polymer matrix shifted to the higher temperatures. For the sample containing 0.6 wt%, an increase of 171% in modulus and a 258.4% enhancement of tensile strength were achieved. Also, elongation at break increased 28.7% at this loading. In fact, intrinsic properties of nanotubes caused enhancement of strength and flexibility simultaneously. Also, for this composite, T_onset and T_max enhanced remarkably and weight loss reduced greatly and residue at 600°C increased to high values. These results are promising for application of the PVB in industry.     

Novel grasshopper protein/soy protein isolate/pullulan ternary blend with hesperidin derivative for antimicrobial edible film

As a green agricultural resource and a new alternative protein, edible insects have the potential to become an excellent source of biopolymer. In this study, a new ternary blend composites were formed based on the mixture of edible grasshopper protein and soybean protein isolates by adding pullulan (PUL). The combined effect of incorporation of antimicrobial agent methyl hesperidin (2.5 %, 5 %, 7.5 % and 10 %) was investigated. The addition of PUL can greatly improve the tensile strength of protein blend composites but has no positive impact on elongation at break. 5 % methyl hesperidin can further increase tensile strength to 7.36 MPa with no deterioration on elongation at break. The SEM and XRD results showed good compatibility between PUL and protein blend. The WVP and WCA results showed that the hydrophobicity of composites increased slightly. Moreover, thermal analysis presented that the thermal stabilities of composites were impaired. The increasing of methyl hesperidin content enhanced antibacterial activity against E. coli and S. aureus of ternary blend film, proving its application value as active packaging.     

Tensile and flexural properties of polypropylene composites filled with highly effective flame retardant magnesium hydroxide

The reinforcing effects of highly effective flame retardant magnesium hydroxide (FMX) content on the tensile and flexural properties of filled polypropylene (PP) composites were investigated within the FMX weight fraction range from 5 to 60 wt%. It was found that the Young's modulus and flexural modulus increased approximately linearly while the tensile yield strength and tensile fracture strength decreased slightly with increasing the FMX weight fraction. When the FMX weight fraction was lower than 20%, the tensile elongation at break decreased considerably, and then decreased slightly; the flexural strength increased when the FMX weight fraction was lower than 30%, and then decreased slightly. The tensile properties increased with increasing rate of tension. Moreover, the tensile yield strength of the composites was estimated using an equation proposed in previous work, and good agreement was shown between the predicted and the measured data.     

沉淀法制备EPDM-g-MAH/CaCO_3复合材料及其性能的表征

提供了三元乙丙橡胶(EPDM)交联的一种方法.以二甲苯为溶剂,溶液法制备马来酸酐(MAH)接枝EPDM,然后向溶液中加入适量碳酸钙(CaCO3),与已接枝的马来酸酐(MAH)反应.待反应完全后,滴加丙酮作为沉淀剂,沉淀物真空干燥,制得EPDM-g-MAH/CaCO3弹性体复合材料.溶解、溶胀及拉伸性能测试结果表明,复合材料样品已形成有效的交联,且材料的抗张强度、断裂伸长率和模量均得到较大幅度的提高,当CaCO3含量达到体系总重的20%时,复合材料呈现最佳力学性能.上述实验结果是因为碱性的CaCO3的Ca2+可以与接枝在EPDM上的MAH发生配合反应,进而成为EPDM的交联中心,形成有效交联,从而促进了EPDM机械性能的提高,ATR-FTIR和TGA的测试结果被用于证实上述观点.     

Effect of air change rate on rubber accelerated ageing tests in hot air. Part 2. Ageing of different compounds

Seven different compounds based on NR, SBR, NBR and EPDM were aged at 100 and 125°C, and 3, 6.5 and 10 changes of air per hour, and in a normal oven at much lower air change rate at 100 °C. Ageing was evaluated by tensile strength, elongation at break, stress at intermediate elongation and changes of IRHD after ageing. The statistical analysis of results shows that air change rate has a significant effect on ageing results.     

Ribbon-like microfiber of vulcanized and non-vulcanized natural rubber obtained by the solution blow spinning

Natural rubber (NR) microfibers were obtained from NR/chloroform solutions with or without vulcanization agents, by a solution blow spinning (SBS) technique. The microfibers showed a ribbon-like morphology with average widths ranging from 15 to 45 μm, depending on the processing conditions. Concentrations of 3%, 4%, and 5% (wt/vol) of NR/chloroform were compared; at 4% wt/vol the spinning process was most stable, and fiber width was the most homogeneous. Microfibrous NR membranes incorporating vulcanizing agents were treated at temperatures of 70, 80, and 90°C for 1, 2, 3, and 4 h. Membrane tensile strength and elongation at break varied with temperature and treatment time. The best result was found with the sample treated at 90°C for 3 h. In this case, the tensile strength and elongation at break was (4.9 ± 0.8) MPa and (867 ± 18) % which is about 310% and 330% higher than the values found for the same sample without the incorporation of vulcanizing agents. This expressive increase was attributed to the vulcanization of the rubber, which also provided a shift to a higher value of the glass transition temperature. Overall properties of the blow-spun films, especially the high elasticity-contraction, suggest they are attractive candidates for use in robotics, and biobased electronics including wearable sensors.     

对苯乙烯磺酸钠改性炭黑对天然橡胶胶乳力学性能的影响

在Haake转矩流变仪的热机械作用下,用对苯乙烯磺酸钠(NASS)对炭黑进行预处理,制备了在水介质中具有优异的分散稳定性的亲水性纳米炭黑粒子(PNASS-CB),并将其直接用于天然橡胶胶乳的补强研究.1HNMR和FT-IR结果表明NASS在炭黑表面成功聚合包覆,用热重分析方法计算其包覆率为8.1 wt%,接枝率为2.5 wt%.亲水性炭黑的表面自由能降低,同时,Payne效应和结合胶含量表明亲水性炭黑粒子与橡胶的相互作用强于亲水性炭黑粒子之间的相互作用.因此,亲水性炭黑/天然橡胶胶乳复合材料的硫化时间变短,转化速度加快,硫化胶的撕裂强度提高了85%,拉伸强度提高了30%,断裂伸长率提高了20%.     

Study of viscoelastic properties of white carbon black reinforced synthetic polyisoprene

The viscoelastic properties of synthetic polyisoprenes(PI) reinforced by white carbon black(WCB) have been investigated and compared with WCB reinforced natural rubber(NR), including cure characteristics, physio-mechanical and dynamic mechanical properties. Compared with NR, PI loaded with the same amount of WCB(PI/WCB) exhibited shorter scorch time and optimal cure time, indicating that WCB fillers are comparatively easier to conjugate with PI. The tensile strength and elongation at break decreased with WCB filling in both PI and NR vulcanizates. The hardness of the rubber vulcanizates increased with the WCB filling in the rubber matrix. PI/WCB blends exhibited smaller hardness data, lower tensile strength, as well as lower elongation at break and tensile stress. Increasing the amount of WCB in rubber matrix induced the Payne effect. However, the Payne effect is much more obvious for the PI/WCB system, and PI/WCB also displayed higher storage modulus whereas lower loss modulus and loss tangent than NR/WCB, which could all be attributed to the poor dispersibilities of WCB in the PI matrix.     

BaTiO3 / (PU/UP-IPNS)复合材料的相容性、力学性能和阻尼性能研究(英)

以水热法合成的BaTiO3纤维和同步法制备的互穿聚合物网络为原料，采用原位分散聚合法获得了一系列BaTiO3/(PU／UP-IPNs)复合材料。采用傅立叶交换红外分光光度计跟踪考察了IPNs的聚合过程，用透射电镜观测了IPNs及其复合物的形貌。结果表明，IPNs中两相相畴尺寸在纳米级范围内，在此基础上，实现了BaTiO3纤维状的复合。动态力学性能的检测结果表明，相较纯IPNs，复合材料的阻尼损耗模量和阻尼损耗因子值均有所提高，且在低温区均出现了肩峰。复合物的最大损耗因子值均大于0．4，在约50℃范围内，E’值提高100MPa。力学性能检测结果表明，IPNs中的连续相是决定材料力学性能的主要因素；有机／无机组分间混溶性的降低，使BaTiO3/IPNs复合材料的抗张强度和断裂伸长率均下降。