FTIR研究PVC热塑性弹性体分子间相互作用及结晶行为

用FTIR研完了PVC/DOP/NBR热塑性弹性体中分子间的相互作用及PVC的结晶行为。结果表明,PVC分子的结晶振动谱带受加入的增塑剂(DOP)和橡胶(NBR)的影响而减弱,PVC中—C—CI基团与DOP分子中的—C=0基团存在相互作用,而PVC中α-H原子与NBR的C=N基的相互作用是PVC与NBR相容的分子基础。     

炭黑表面修饰对填料网络化的影响

炭黑加入到橡胶后会导致橡胶动态粘弹性发生很大变化,填料网络化是决定填充橡胶动态滞后的主要原因,文中采用含有吡啶官能团的分子对炭黑N330进行表面修饰,以控制炭黑填充橡胶的动态粘弹行为。结果发现,炭黑表面经过修饰后,增大了炭黑聚集体在橡胶中的平均距离,并使炭黑的网络化程度得到控制。通过对两种炭黑填充橡胶相对模量的研究,发现在动态应变的作用下,改性炭黑(GCB)之间的填料网络更容易受到破坏。说明炭黑经过表面修饰后,其表面能降低,炭黑粒子之间的相互作用减弱。     

炭黑表面修饰对填料网络化的影响EI北大核心CSCD

炭黑加入到橡胶后会导致橡胶动态粘弹性发生很大变化,填料网络化是决定填充橡胶动态滞后的主要原因,文中采用含有吡啶官能团的分子对炭黑N330进行表面修饰,以控制炭黑填充橡胶的动态粘弹行为。结果发现,炭黑表面经过修饰后,增大了炭黑聚集体在橡胶中的平均距离,并使炭黑的网络化程度得到控制。通过对两种炭黑填充橡胶相对模量的研究,发现在动态应变的作用下,改性炭黑(GCB)之间的填料网络更容易受到破坏。说明炭黑经过表面修饰后,其表面能降低,炭黑粒子之间的相互作用减弱。     

炭黑—弹性体间的相互作用研究

为探讨被粘橡胶配方中炭黑的结构性对金属－橡胶硫化粘接复合体录离强度各向异性影响的作用机理，采用Ｈａａｋｅ Ｒｈｅｏｃｏｒｄ９０流变仪对数种炭黑填充ＮＲ的流化特性进行了研究。结果表明，其最大扭矩及扭矩积分曲线增加速度的变化趋势与结合橡胶含量的变化规律相一致，并与金属－橡胶粘胶粘接体双向剥离比随炭黑的结构性及填充量的依赖曲线具有很好的对应性。并探讨了炭黑活性表面与ＮＲ分子间的相互作用，认为炭黑与ＮＲ间     

可食性大豆分离蛋白/改性纤维素共混膜的性能

研究了不同质量百分数的甲基纤维素(MC),羟丙基纤维素(HPC),羟丙基甲基纤维素(HPMC)对大豆分离蛋白(SPI)膜性能的影响。结果表明,改性纤维素的基团类型和添加质量百分数均对SPI膜的性能产生显著影响。在SPI膜中添加MC、HPC和HPMC后,膜的透光率持续降低;但膜的拉伸强度明显增加,且添加相同质量百分数的HPC、MC、HPMC对膜拉伸强度的增强依次增加;膜的表面疏水性持续增大,增大的幅度依次为MCHPMCHPC。特别在添加MC后,在膜的拉伸强度增强的同时,膜的伸长率也提高。这表明改性纤维素中不同的基团决定了纤维素分子链间及其与SPI分子链间的相互作用,从而改变了SPI分子链间的相互作用。     

秸秆纳米纤维素与炭黑补强天然胶的界面作用

基于橡胶复合材料的力学性能、交联密度、粘弹行为、热行为、动态性能和形貌结构,利用红外光谱(FT-IR)、X射线光电子能谱(XPS)、差示扫描量热分析、动态力学分析等对酚醛树脂(PF)改性前后秸秆纳米纤维素(SNC)与炭黑(CB)补强的天然橡胶(NR)的界面影响进行了系统分析,并对SNC,PF与NR的成键形式进行了理论分析。FT-IR分析表明SNC-PF上的羟基(-OH)吸收峰发生了蓝移,XPS谱图中显示改性后SNC中O1s结合能升高,说明SNC与PF之间具有强的氢键作用。与NR/CB/PF体系相比,NR/CB/SNC/PF体系在大形变下具有更高的弹性模量(G′),说明其具有更强的橡胶交联网络,该体系具有更高的受限橡胶层质量分数(χ_(im)),说明该材料存在更厚的受限橡胶分子层,意味着其填料更好地分散和填料-基体间更强的相互作用。而NR/CB/SNC/PF复合材料较低的损耗因子(tanδ)、较高的填料-基体间相互作用参数和大应变下较高的上扬临界值(λ~(-1)),都表明其中的填料与NR之间具有更强的相互作用。扫描电镜(SEM)显示PF的加入使填料包埋在NR基体中,且分散更均匀。说明PF的加入使CB/SNC(填料网络)与NR基体形成互穿聚合物网络,填料与NR基体的相互作用增强,交联密度增加,而使CB补强NR的力学性能得到保持或改善。     

含非线性生色团取代聚丙烯酸酯的溶液性质

研究高分子的分子结构以及链结构行为和规律,对材料设计和应用有极为重要的意义。采用凝胶渗透色谱示差折光指数(RI)/黏度(DV)/激光光散射(RALLS)三检测联用技术,研究了非线性光学聚合物———侧链型聚丙烯酸酯的溶液性质,详细分析了侧链刚性共轭结构以及刚性共轭基团与主链之间连接链的方式与结构对高分子特性粘数、均方旋转半径0/M和Flory特征比C∞的影响。结果发现侧链共轭结构长度增加将增大分子的无扰尺寸和Flory特征比;主链与共轭基团间通过柔基团连接时,分子无扰尺寸和Flory特征比降低。     

炭黑表面改性对HAF／NR复合材料动态粘弹性的影响

采用含有吡啶官能团的分子对高耐磨炭黑粒子HAF进行改性.利用橡胶加工分析仪(RPA2000)研究了炭黑填充天然橡胶的非线性动态粘弹行为,结果发现,改性炭黑增强了填料-橡胶之间的相互作用,减弱了填料-填料之间的相互作用.而且利用时温等效原理研究了硫化胶在高频下的动态粘弹行为,发现改性炭黑增加了在10.4 Hz～10.6 Hz的损耗因子,减小了在10 Hz～100 Hz的损耗因子.     

离子液体作为多功能助剂在白炭黑填充天然橡胶中的应用

以天然橡胶为基体,探究了离子液体对橡胶硫化、白炭黑分散性及白炭黑与橡胶界面相互作用的影响,对比了离子液体用量及烷基链长度对白炭黑填充天然橡胶的作用效果。通过硫化机理的研究及硫化特性的对比发现,溴化咪唑盐离子液体能够活化硫化反应,极大地提高了硫化速率和交联密度。离子液体与白炭黑之间存在离子偶极相互作用,佩恩(Payne)效应结果表明,离子液体能够改善白炭黑在天然橡胶中的分散,且随着用量及咪唑环烷基链长度的增加,改善效果越来越明显。通过结合胶含量测定和拉伸断裂表面观察可以得出,离子液体能够改善橡胶与填料的界面相容性。在离子液体3种功能的共同作用下,白炭黑填充天然橡胶复合物的拉伸强度最大增加了114%,撕裂强度最大增加了201%,邵坡尔(DIN)磨耗损失最大减少了50%;用量为3 phr时,硫化胶的各项力学性能最佳。     

炭黑与大小橡胶粒子的相互作用及其受停放时间的影响

采用反复离心纯化的方法制备出大、小橡胶粒子的胶乳样品,干燥得到天然橡胶生胶,与炭黑混炼得到相应混炼胶,研究了各样品与炭黑的相互作用及其随停放时间的变化。研究表明,小橡胶粒子胶乳所制备的天然橡胶相应混炼胶中结合胶含量较高,随停放时间延长,添加了小橡胶粒子的样品结合胶含量先上升后下降,大橡胶粒子样品结合胶含量则持续上升;扫描电子显微镜的分析结果表明,小橡胶粒子胶乳所制备的天然橡胶中炭黑分散性差,炭黑与橡胶基体相容性差,存在较多附聚体,大橡胶粒子胶乳所制备的样品中炭黑分散性则较优。差示扫描量热仪对结合胶玻璃化转变特性的分析表明,各结合胶样品在玻璃化转变前后的比热流差值随停放时间的延长先增大后减小,这是由于样品中的橡胶连续相先增加后减少。总而言之,小橡胶粒子胶乳所制备的天然橡胶相应混炼胶中所测结合胶含量更高,但与炭黑相容性差,多为受限于填料内部的包覆橡胶。     

Investigation on the dispersion of carbon nanotubes in nitrile butadiene rubber: Role of polymer-to-filler grafting reaction

This contribution reports on the dispersion by simple melt blending of tiny amounts of carbon nanotubes (CNT) in nitrile butadiene rubbers (NBR). Acrylonitrile (ACN) units of NBR are known to generate free radicals upon heating and/or shearing. This paper highlights elements evidencing a possibility for NBR polymer chains to react by a free-radical mechanism and to graft onto CNT surface all along the process of mechanical blending of NBR with CNTs. More precisely and since the formation of the free-radicals takes place on the ACN units, the influence of the ACN relative content in NBR on the grafted CNT amount has been studied. It comes out that the polymer-grafting rate onto the CNT surface increases with the ACN content in NBR. Interestingly, the nanotubes proved more finely dispersed in NBR containing higher relative ACN content as evidenced by morphological observations as well as electrical measurements.     

丙烯腈含量对NBR混炼胶硫化反应的影响

采用差示扫描量热法(DSC)研究了丙烯腈(AN)含量和炭黑对丁腈橡胶(NBR)硫化反应的影响。研究表明,AN含量由18.8%(质量分数,下同)增加至43.3%,硫化胶的物理交联密度增加约20%,化学交联密度大大增加,增加约73%。NBR复合材料的硫化反应分两个阶段:第一阶段硫磺硫化反应,第二阶段硫键短化和双键交联反应。AN含量增加,两阶段分离明显,硫化温度降低,第一阶段放热量减小,第二阶段放热量增加。炭黑加入后,催化了硫化反应,提高了化学交联密度,降低了反应热,且起始硫化温度受丙烯腈含量的影响变小,由未加炭黑的34℃降低到12℃。此外,丙烯腈含量越低,硫化反应受炭黑的影响越大。     

Gamma irradiation aging of NBR/CSM rubber nanocomposites

The effect of gamma-irradiation on the acrylonitrile butadiene/chlorosulphonated polyethylene rubber blends (NBR/CSM) based nanocomposites containing carbon black (CB) and silica filler (Si) were investigated by TG-DTG and ATR-FTIR techniques. The silica (with primary particle size of 22 nm) was added in content of 0, 10, 20 and 30 phr and carbon black (with primary particle size 40–48 nm) was added in content of 30 phr and rubber blend compounds were prepared. The obtained elastomeric materials were aging to different γ-irradiation doses (100, 200 and 400 kGy). The cure and mechanical properties of obtained nanocomposites were determined. Incorporating 20 phr of silica to the control NBR/CSM rubber blends containing 30 phr CB resulted 152% increase in tensile strength, 116%, in elongation at break and 142% modulus at 100% elongation, according to synergistic effect between the fillers. FTIR measurements of aged samples estimated the formation of alcohols, ethers and small amounts of lactones, anhydrides, esters and carboxylic acids after exposure to lower doses of γ-radiation (100 kGy). On the basis of the obtained spectra the formation of shorter polyene sequences and aromatic rings in aged elastomeric samples are assumed. The results show that 30 phr of carbon black (CB) and 20 phr of silica are needed for the best gamma aging resistance of NBR/CSM rubber nanocomposites. The result of radiation exposure is decrease in mechanical properties. The dose at which ultimate mechanical properties decreased was at 200 kGy. TG-DTG measurements estimated decrease in thermal stability of gamma-irradiated NBR/CSM rubber blend based nanocomposites. Silica reinforced NBR/CSM rubber blend had better radiation resistant than carbon black. Rough and heterogeneity of fracture surfaces has been observed for NBR/CSM rubber blends filled with silica. More uniform morphology of fracture surfaces according to high polymer–filler interaction and low filler–filler interaction has been observed for CB/Si filled NBR/CSM rubber blend.     

基于傅里叶变换红外光谱的航空丁腈橡胶鉴别方法

介绍了航空丁腈橡胶(NBR)的编号规则,分析了傅里叶变换红外光谱(FTIR)定量法鉴别航空丁腈橡胶的理论依据。将航空丁腈橡胶试样经无水乙醇萃取、烘干后,采用红外光谱定量法统计分析了光谱中特征吸收峰(-C≡N基与-CH=CH₂基)的吸光度比值R与橡胶生胶丙烯腈(CAN)含量的半定量对应关系和鉴别橡胶的种类。结果表明:生胶丙烯腈含量越高,特征峰吸光度比值R越大,具有线性对应关系。依据R推断丁腈橡胶的生胶类型,再结合橡胶硫化硬度,可对航空丁腈橡胶作进一步鉴别。对于不同类型生胶并用的丁腈橡胶而言,并用胶的某些特征官能团可作为橡胶鉴别的依据。     

橡胶微观结构因素对声障板吸声性能的影响

选择丁苯橡胶(SBR)和丙烯腈(CN)含量为36%~41%的丁腈橡胶(NBR),分别与氯化丁基橡胶(CIIR)共混,研究了SBR和NBR两种橡胶由于微观结构不同对声障板吸声性能的影响。由于微观结构的差异,SBR与NBR相比,其与丁基橡胶的共混(并用)胶料在0.5~3 MPa静水压力和3.5~7 k Hz频率范围条件下,吸声性能对静水压力的敏感性较低,且在试验的整个静水压力范围和频率范围尤其在1.5~3.5 k Hz频段具有更高的吸声性能。     

滑动接枝共聚物/丁腈橡胶复合材料及其阻尼性能

将丁腈橡胶（NBR）与预硫化滑动接枝共聚物（SGC）混合制备SGC/NBR复合材料,并采用DSC、橡胶加工分析仪（RPA）、TEM和FTIR等研究了预硫化温度对复合材料内部结构及动态力学性能的影响。结果表明:SGC作为分散相在NBR基体中形成了海岛结构,且与NBR 大分子之间形成了分子间氢键,使两相相容性较好并形成了明显的界面作用区。界面作用区的存在使SGC/NBR复合材料的玻璃化转变温度与纯NBR基体相比升高,同时使复合材料的拉伸强度和拉断伸长率等力学性能显著增强,并出现了明显的拉伸取向。由于SGC与NBR之间分子链的扩散以及氢键作用,使分子链σ单键的内旋转受阻,旋转时需要消耗能量以克服所受的阻力,造成SGC/NBR复合材料的损耗因子明显增加,其中预硫化温度为160℃时阻尼效果最好。SGC/NBR复合材料在建筑桥梁振动频率应变变形范围内表现出优异的损耗性能,可应用于高阻尼隔震支座。      

Preparation and properties of nitrile rubber/montmorillonite nanocomposites via latex blending

The nitrile rubber (NBR)/unmodified montmorillonite (Na-MMT) clay nanocomposites were prepared by latex blending method followed by melt mixing of compounding ingredients by using two-roll mill. The X-ray diffraction (XRD) studies showed an increase in the basal spacing and broadening of peak corresponding to crystal structure of Na-MMT indicating the formation of intercalated/exfoliated clay layers in the NBR matrix. Increase in clay content of nanocomposite increased the XRD peak height due to the formation of many of clay tactoids at higher loading. The transmission electron microscopy (TEM) strengthened the XRD finding by showing the presence of intercalated/exfoliated morphology of clay platelets having good dispersion. The modulus and tensile properties of the nanocomposites were improved with addition of Na-MMT which is proportional to clay concentration. The retention of tensile properties of aged nanocomposites, with all clay concentration, was superior to either pure NBR and carbon black filled NBR composite. The dynamic mechanical analysis showed proportional increase in storage modulus analogous to Na-MMT loading at all the temperature ranges due to the confinement of polymer chains between the clay layers. Nanocomposites with different proportions of clay showed a decrease in tan δ_max peak height with a shift towards higher temperature indicating the reduction in the segmental mobility of polymer chain. A linear model was proposed to correlate the influence of Na-MMT content on storage modulus of nanocomposites. Differential scanning calorimetry indicated a linear increase in glass transition of nanocomposites which is proportional to clay loading. Thermogravimetric analysis revealed a small improvement in the thermal stability of nitrile rubber/clay nanocomposites.     

Effect of grafting cellulose acetate and methylmethacrylate as compatibilizer onto NBR/SBR blends

Compatibilizer is used for improving of processability, interfacial interaction and mechanical properties of polymer blends. In this study acrylonitrile butadiene rubber (NBR) and styrene-butadiene rubber (SBR) blends were compatibilized by a graft copolymer of acrylonitrile butadiene rubber (NBR) grafted with cellulose acetate (CA) i.e. (NBR-g-CA) and acrylonitrile butadiene rubber (NBR) grafted with methylmethacrylate i.e. (NBR-g-MMA). Compatibilizers were prepared by gamma radiation induced grafting of NBR with cellulose acetate (CA) and methylmethacrylate (MMA) were added with different ratios to NBR/SBR (50/50) blend. The compatibilized blends were evaluated by rheometric characteristics, physico-mechanical properties, swelling behavior, scanning electron microscope (SEM) and thermal analysis. The results showed that, the blends with graft copolymer effect greatly on the rheological characteristics [optimum cure time (Tc₉₀), scorch time (Ts₂), and the cure rate index (CRI)]. The physico-mechanical properties of the investigated blends were enhanced by the incorporation of these graft copolymers, while the resistance to swelling in toluene became higher. SEM photographs confirm that, these compatibilizers improve the interfacial adhesion between NBR/SBR (50/50) blend which induce compatibilization in the immiscible blends. The efficiency of the compatibilizer was also evaluated by studying the thermogravimetric analysis.     

丁腈橡胶/导电粒子复合材料的正温度系数(PTC)特性

将导电粒子碳黑和铜粉分别与丁腈橡胶混合制备导电聚合物复合材料，其中碳黑（Ｎ５５０）／丁腈橡胶复合材料的电阻率随温度的变化呈现较强的正温度系数（ＰＴＣ）效应。讨论了掺入导电粒子浓度、结构和表面性质以及混炼硫化工艺等对该类材料的室温电阻率及ＰＴＣ效应的影响。     

混炼工艺对SBR/BR/CB共混硫化胶性能的影响

为了研究混炼工艺对最终硫化胶性能的影响,利用HAAKE转矩流变仪对不同配比的丁苯橡胶/顺丁橡胶/炭黑进行混炼,混炼采用两种不同的混炼顺序——一种是炭黑首先与丁苯橡胶(SBR)混炼,然后加入顺丁橡胶(BR)混炼;另一种是BR与炭黑混炼之后再加入SBR进行混炼。对制得共混物进行结合胶含量、拉伸以及动态力学性能测试。结果显示,在相同配比下,炭黑首先跟份数多的富相橡胶混炼可以得到较多的结合胶,有利于体系的补强;动态力学测试结果表明硫化胶的粘弹特性受第一段混炼所用橡胶的影响较大,炭黑与柔顺性较好的BR先混炼,共混体系工艺相容性较好。