超临界CO2制备三元乙丙橡胶微孔泡沫

本工作采用超临界CO2作为物理发泡剂,通过快速泄压法制备了三元乙丙橡胶(EPDM)微孔泡沫材料,并系统深入地研究了发泡条件及硫化条件对EPDM泡沫结构等方面的影响.通过一系列的实验发现:硫化条件决定EPDM基体的强度、交联度以及弹性,是泡孔结构形成的关键因素,预硫化程度过高或过低都不利于形成较好的泡孔结构;scCO2饱和温度降低有利于制备孔径更小的泡孔;scCO2饱和压力的增大明显改善了泡孔形貌的规整度,提高了泡孔的均匀性,泡孔的密度随饱和压力的升高而呈指数级增加;不同硫化条件和发泡条件下制得的EPDM基微孔泡沫,其最小平均孔径达到了1.24μm,最大孔密度达到了1.33×1011个/cm3.     

双峰结构硅橡胶泡沫的制备

通过超临界CO_2发泡制备了MMT-SiO_2/MVQ复合泡沫材料。研究了MMT对硅橡胶复合体系流变性能,以及成核机理的影响,并且系统的研究了发泡工艺对泡孔形貌的影响。结果表明,MMT对硅橡胶基体补强作用较弱,在基体中与白炭黑均作为异相成核剂,发生异相成核,从而获得具有双峰泡孔结构的硅橡胶泡沫。此外,通过优化工艺参数可以获得更好的微孔硅橡胶泡沫。     

一种制备均孔三元乙丙橡胶泡沫材料的新方法

三元乙丙橡胶(EPDM)泡沫材料是一种综合性能优异的新型功能材料,其常规制备过程复杂,需要加入大量配合剂,难以获得均匀、细小的泡孔结构。本研究提出一种新的制备方法,即采用辐射化学法,以炭黑为补强填料,在室温下对三元乙丙橡胶胶料进行辐射硫化,再模压发泡,制备炭黑填充型三元乙丙橡胶泡沫材料,并分析产物的微观结构和相关性能。研究结果表明,辐射化学法EPDM泡沫材料的泡孔分布均匀,平均胞体孔径仅为16μm,拉伸强度高达1.7MPa。     

Si-69在白炭黑填充的EPDM硫化胶中的补强作用

本文用溶胀法测定了白炭黑填充的EPDM硫化胶中橡胶-填料间的相互作用程度。试验结果表明:硅烷偶联剂Si-69具有增强聚合物-填料间相互作用的能力。从凝胶含量,物理性能等方面,进一步证实了Si-69在白炭黑填充的三元乙丙胶中具有一定的补强作用。     

纳米二氧化硅对微交联三元乙丙橡胶的交联行为和物理发泡行为的影响研究

通过高压CO_2流体物理发泡方法制备了微交联的三元乙丙橡胶(EPDM)纳米复合泡沫材料。研究了EPDM/SiO_2纳米复合材料的交联动力学,纳米复合发泡材料的发泡倍率、泡孔形貌及拉伸性能,探讨了纳米粒子对EPDM交联行为和物理发泡行为的影响。研究结果表明,纳米SiO_2的添加加快了EPDM的交联速率,但降低其交联程度;同时,纳米SiO_2添加量的增加提高了EPDM发泡材料的膨胀倍率至10.3倍,加强了泡孔成核,使泡孔密度从10~5个/cm~3增加至10~8个/cm~3,提高了发泡材料的拉伸性能,其中拉伸强度从0.75MPa提升至1.65 MPa,断裂伸长率从225%提升至423%。不过,当添加量为5phr时,纳米SiO_2对EPDM的发泡行为及其发泡材料的拉伸性能产生负面影响。所制备的EPDM/SiO_2复合发泡材料具有微交联结构,模压后的薄膜可再次进行物理发泡。     

LLDPE/EPDM共混物的超临界CO2微孔发泡研究

研究了线性低密度聚乙烯(LLDPE)/三元乙丙橡胶(EPDM)橡塑共混物在超临界CO_2中的微孔发泡行为。利用扫描电子显微镜对发泡样品的泡孔形貌进行了分析和表征;采用差示扫描量热仪分析了共混物的热性质;分别利用旋转流变仪和万能试验机分析得到样品的流变性能和力学性能。采用一定量的LLDPE与EPDM共混,压制标准试样,然后在高压反应釜中进行发泡,讨论了LLDPE/EPDM共混物中橡塑的质量比、饱和温度、饱和压力对材料泡孔结构和泡孔均匀性的影响。利用超临界CO_2作物理发泡剂,对发泡条件进行优化,可得到泡孔尺寸规整、泡孔密度高且回弹性和韧性较好的发泡闭孔材料。     

动态硫化三元乙丙橡胶/聚丙烯橡胶:流变、结晶和动态力学性能

运用动态硫化法制备EPDM/PP橡胶,研究了其流变行为、结晶及动态力学性能。利用扫描电镜观察了硫化EPDM/PP橡胶熔融共混后EPDM颗粒在PP基体中的分散情况。动态力学性能(DMA)和拉伸性能测试的结果显示橡塑比为40/60时,EPDM/PP橡胶的综合性能最为优异。研究了硫化EPDM/PP橡胶在黏性弹性区域的振荡剪切行为。DMA结果显示橡塑比提高导致储能模量与tanδ下降。流变行为表明,复合黏度随交联密度的增加而增加,弹性变形优于黏性流动。硫化过程使EPDM颗粒细化导致PP分子链结晶受阻。     

EPDM/PP热塑性弹性体研究进展

对动态硫化EPDM /PP热塑性弹性体的研究作了简要回顾 ,介绍了动态全硫化制备EPDM /PP热塑性弹性体的方法 ,重点讨论在动态硫化中影响EPDM /PP热塑性弹性体的力学性能、流变性能、相态结构和结晶性能的一些因素     

聚丙烯种类对硅烷交联PP/POE(EPDM)共混材料性能的影响

目的 针对聚丙烯原料的选择对硅烷交联PP/POE(EPDM)共混材料性能的影响,进行系统的研究分析。方法 固定PP和POE(EPDM)的质量比为70∶30,添加VTMS,DCP,DBTDL的质量分数为1.5%,0.1%和0.1%,制备分别以PP-B和PP-H为基体材料的硅烷交联共混材料;研究2种共混材料的凝胶含量、结晶行为、流变性能、力学性能、微观结构等的差异,分析不同基体聚丙烯对硅烷交联聚丙烯共混材料力学性能产生影响的原因。结果 虽然PP-B的性能优于PP-H,但与POE(EPDM)硅烷交联后,PP-H在力学性能、热稳定性等方面优于PP-B,PP-B的交联程度更高。结论 在PP/POE(EPDM)硅烷交联材料的选择中,为了达到节省资源,并获得最佳性能的目的,应充分考虑聚丙烯原料种类对共混材料性能的影响,以选择出最优方案。     

EPDM对VMQ硅橡胶泡沫发泡行为及力学性能的影响

本工作采用超临界二氧化碳(scCO₂)发泡技术制备甲基乙烯基硅橡胶(VMQ)/三元乙丙橡胶(EPDM)复合发泡材料，探讨了预硫化时间、EPDM含量以及饱和温度对泡孔形貌的影响。力学性能测试结果表明硅橡胶泡孔结构和EPDM含量对复合材料力学性能有较大影响。当预硫化时间为8 min时，其交联密度为2.7×10^-5mol·cm^-3,可得到较好发泡性能和较宽发泡窗口。在60℃饱和温度、10 MPa饱和压力下发泡的VMQ-0.5EPDM(每100份硅橡胶中加入0.5份EPDM)密度可以达到0.2 g/cm³(发泡倍率为5.7倍);同时，参考VMQ-0EPDM,VMQ-0.5EPDM的比压缩强度从1.88 MPa·cm³/g增加到2.51 MPa·cm³/g,提升33%。     

耐高温硅橡胶的配方研究

为提高硅橡胶的耐高温性能,确定最佳的实验配方,以乙烯基硅橡胶为基础胶,八氢基笼型倍半硅氧烷(T_8H_8)为交联剂,白炭黑为补强填料,纳米级氧化锡为耐热填料,制备出一种耐高温硅橡胶.该配方中T_8H_8为自行合成的耐高温硅橡胶交联剂,通过红外光谱(FTIR)、X射线衍射(XRD)、核磁共振氢谱(1HNMR)对T_8H_8结构进行表征,探究了不同配方对硅橡胶耐热性能的影响.结果表明,当乙烯基硅油用量为100 phr,T_8H_8中Si—H与乙烯基硅橡胶中Si—Vi的摩尔比为4∶1,白炭黑添加量为15 phr,氧化锡添加量为8 phr时,硅橡胶的初始分解温度达到489.77℃,拉伸强度为4.06 MPa,剪切强度1.69 MPa.     

三元乙丙橡胶耐磨性能研究

研究了生胶品种、硫化体系、填充体系和加工助剂等因素对三元乙丙橡胶耐磨性能的影响。实验结果表明:胶种选用高乙烯含量,高门尼粘度的非充油型乙丙橡胶,硫化体系采用硫磺/硫载体并用的有效硫磺硫化体系,填充体系采用高结构炭黑N220以及Si-69改性过的气相法白炭黑AS-200并用体系,同时配合0.5份左右的爽滑粉,都能有效提高EPDM胶料的耐磨性能。     

Quantitative mapping of surface elastic moduli in silica-reinforced rubbers and rubber blends across the length scales by AFM

The surface elastic moduli of silica-reinforced rubbers and rubber blends were investigated by atomic force microscopy (AFM)-based HarmoniX material mapping. Styrene–butadiene rubbers (SBR) and ethylene–propylene–diene rubbers (EPDM) and SBR/EPDM rubber blends with varying concentrations of silica nanoparticles (0, 5, 10, 20, 50 parts per hundred rubber, phr) were prepared to investigate the effect of different composition on the resulting morphology, filler distribution and elastic moduli of a specific rubber or rubber blend sample. For SBR, the elastic modulus values varied from 0.5 MPa for unfilled SBR to 5 MPa for 50 phr reinforced SBR with the increase in the concentration of filler. For EPDM, the corresponding values increased from 1.4 MPa for unfilled EPDM to 4.5 MPa for 50 phr reinforced EPDM. Local stiff and soft domains in silica-reinforced SBR and EPDM rubbers and rubber blends were identified by HarmoniX AFM imaging. While the stiff silica particles show modulus values as high as 2 GPa, the rubber matrix reveals modulus values in the range of ca. 30 MPa for the rubber blends to ca. 300 MPa for the unfilled rubbers. The lower value of elastic modulus of the EPDM phase in the blend, compared to the blank EPDM compound can be attributed to the presence of Sunpar oil in the compound which has a very good affinity with EPDM and decreases the rubber modulus. The elastic moduli maps revealed an increase of the areal fraction of silica particles showing an intrinsic surface modulus value with rising silica content in the compound preparation mixture. HarmoniX AFM measurements revealed the formation of larger silica aggregates in EPDM in contrast to SBR where isolated silica particles were observed. For silica-reinforced rubber blends a phase separation into a soft (ca. 40 MPa) and a significantly harder phase could be observed (ca. 500 MPa–1.5 GPa) indicating the incorporation of silica particles in the SBR phase. Using HarmoniX AFM imaging significantly higher surface elastic moduli were observed compared to those obtained by bulk tensile testing. Possible reasons for the observed differences between bulk modulus values and those measured by AFM are discussed in detail, including the aspect of different averaging procedures like inherent to surface probing by AFM versus bulk tensile testing, different filler distributions in SBR and EPDM and the AFM modulus calibration procedures.     

The influence of multiscale fillers on the rheological and mechanical properties of carbon-nanotube–silica-reinforced epoxy composite

Multiscale fillers were fabricated through synthesis of carbon nanotubes (CNTs) on silica microparticles by the use of chemical vapor deposition. Three types of catalyst precursors with different concentrations and reaction times were investigated to find the optimal conditions for CNT synthesis. The produced multiscale fillers of CNT–silica were incorporated within epoxy resin to fabricate a multiscale composite. Rheological analysis and tensile and impact tests were performed to study the effect of fillers on the structural properties of composites. The rheological results demonstrated a similar viscous behavior between CNT–silica suspensions and epoxy, which implies that there was no critical increase of viscosity. Significant improvements in the elastic modulus and tensile and impact strength were achieved for epoxy matrix filled with the optimal fraction of multiscale fillers. The reinforcing efficiency of multiscale fillers was evaluated by comparing the results of micromechanical models with experimental data.     

Using the bond energy density to predict the reinforcing ability of a composite

A model is proposed to predict the ability of a filler to reinforce a polymer. The model combines the effects of filler particle size, filler surface chemistry and filler volume fraction into one parameter called the bond energy density. Bond energy density is defined as the total interfacial bond energy per unit volume of a polymer composite. Bond energy density is determined by Fowkes's equation. The critical bond energy density, which is equivalent to the bond energy density of the composite when its tensile strength equals that of its matrix, determines whether a filler will reinforce or weaken a polymer. To get a filler reinforcing effect, the bond energy density of the composite must be greater than its critical bond energy density.     

Effect of aluminium hydroxide,chlorinated polyethylene,decabromo biphenyl oxide and expanded graphite on thermal,mechanical and sorption properties of oil-extended ethylene–propylene–diene terpolymer rubber

Oil-extended EPDM composites with different flame retardant fillers like aluminium hydroxide (ATH), chlorinated polyethylene (CPE), decabromobiphenyl oxide (DBBO) and expanded graphite (EG) were prepared by conventional mill mixing. Thermal, mechanical and sorption characteristics of the vulcanizates were studied. The effect of different fillers on the flammability of the composites was measured using Limiting Oxygen Index (LOI) and UL-94 HB tests. Scanning Electron Microscopic (SEM) studies of the composites were also conducted. ATH and CPE improve the thermal stability of the composite substantially. Among the four fillers ATH has the highest reinforcing effect on the EPDM rubber. Sorption studies of the composite showed that ATH reduced the swelling rate of the microcomposite considerably. All the four fillers were effective in improving the flame retardant property. Filler dispersion studies and SEM images point to a uniform dispersion of filler in the matrix which is in good agreement with significant improvement in mechanical properties.     

Tensile behaviour and fracture toughness of EPDM filled with untreated and silane-treated glass beads

The Essential Work of Fracture (EWF) theory has been applied to study the fracture behaviour of untreated and silane-treated glass bead-filled EPDM composites. The experimental values of both Young's modulus and tensile strength have been compared with those predicted by the main theoretical and semiempirical models, and the influence of the composite processing temperature on the tensile properties has been studied, noticing a marked drop of stiffness and strength from a processing temperature of 200 °C. A good adhesion between EPDM matrix and glass beads was achieved with the silane Z-6032, resulting in higher tensile strength, and it has been observed that glass bead presence induces plasticity in the EPDM matrix. No differences of the specific essential work of fracture were found in the three filled samples, although results show that the higher adhesion degree between matrix and particles, the higher value of the specific plastic work of fracture, and also the higher final instability in crack propagation.     

双辊共混法制备EPDM/OMMT纳米复合材料

自制一种有机改性蒙脱土(OMMT),采用双辊共混法与三元乙丙橡胶复合,得到了具有高强度、低硬度等超常力学性能的乙丙橡胶/有机蒙脱土纳米复合材料。透射电镜观察表明,制备出了半剥离型纳米复合材料,力学性能测试显示,在低填充量(15份以下)时,纳米复合材料的各项力学性能远超过同含量下高耐磨碳黑体系的。在填充量为10份时,有机土填充体系的断裂强度为15.85 MPa,是碳黑填充体系(6.57 MPa)的2.4倍,是纯橡胶体系(2.05 MPa)的7倍多;撕裂强度也高于碳黑体系和纯胶体系的;而此时纳米复合材料的邵A硬度仅为58.5,比相同强度下碳黑补强体系的低近10。     

Evaluation of the influence of nanoparticles' shapes on the formation of poly(lactic acid) nanocomposites obtained employing the solution method

PLA nanocomposites were prepared by adding organically modified montmorillonite clay (Viscogel B8) and a homoionic clay (NT25), as well as unmodified silica (A200) and modified organic silica (R972). All nanocomposites were obtained by the solution intercalation method using chloroform as a solvent. The materials obtained were essentially characterized by X-ray diffraction and low-field nuclear magnetic resonance relaxometry, through the measurement of proton spin-lattice relaxation time (LF-NMR). Both clays and silicas used to obtain the polymeric nanocomposites showed good dispersion in the polymeric matrix. The relaxation times were distinct for each type of nanoparticle used. The nanocomposite formed with homoionic clay, NT25, presented an increase in the relaxation data, indicating formation of intercalated nanocomposites, contrary to the action of the organoclay Viscogel B8, which preferentially formed an exfoliated nanocomposite. When unmodified and organo-modified silica were added to PLA, an increase in the relaxation time of the polymer matrix was observed. According to the relaxation data, the organosilica R972 dispersed better in the polymeric matrix and consequently interacted better than the A200.     

Temperature dependence of the mechanical properties of EPDM rubber-polyethylene blends filled with aluminium hydrate particles

New flame-retardant electrical cables producing no toxic or corrosive gases and smokes when they are exposed to fire are now developed, in particular EPDM rubber-polyethylene blends filled with large amounts of aluminium hydrate particles. The aim of the present work is to study the mechanical behaviour of different filled EPDM-polyethylene blends as a function of temperature. In this first part, the characterization of the initial polymers (EPDM, polyethylene, silane-modified polyethylene) and their corresponding filled blends is presented. Electron microscopical observations reveal that the inorganic particles are embedded in the elastomer phase and consequently are well dispersed within the matrix. Thermal analysis performed by differential scanning calorimetry shows that the characteristics (melting temperatures, degree of crystallinity) of the initial polymers are only slightly affected either when they are mixed together or by the presence of filler. Finally, the variations of the dynamic mechanical moduli of filled blends with the filler volume fraction are in good agreement with the predictions of classical models. The main object of the second paper will be to describe the variation of the static mechanical properties of the blends with temperature and to evidence the causes of an unexpected phenomenon of brittleness which appears at about 70° C.