ELECTRICAL RESISTIVITY,CRYSTALLIZATION AND MECHANICAL PROPERTIES OF POLYPROPYLENE/MULTI-WALLED CARBON NANOTUBE/CALCIUM CARBONATE COMPOSITES PREPARED BY MELT MIXING

Polypropylene(PP)/multi-walled carbon nanotube(MWCNT)/calcium carbonate(CaCO_3)composites are prepared by melt mixing using two types of CaCO_3 of different sizes.The electrical resistivities of the composites with the two types of CaCO_3 are all lower than those of the corresponding PP/MWCNT composites at various MWCNT loadings (1 wt%-5 wt%).The morphology of the composites is investigated by field emission scanning electron microscopy (FESEM).The crystallization behavior of PP in the composites is char...     

Effect of nucleating agent on the brittle–ductile transition behavior of polypropylene/ethylene–octene copolymer blends

In the present work, α‐form nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988) is introduced into the blends of polypropylene/ethylene–octene copolymer (PP/POE) blends to study the effect of the nucleating agent on the toughness of PP/POE blends through affecting the crystallization behavior of PP matrix. Compared with the PP/POE blends, in which the toughness of the blends increases gradually with the increasing content of POE and only a weak transition in toughness is observed, addition of 0.2 wt % DMDBS induces not only the definitely brittle‐ductile transition at low POE content but also the enhancement of toughness and tensile strength of the blends simultaneously. Study on the morphologies of impact‐fractured surfaces suggests that the addition of a few amounts of DMDBS increases the degree of plastic deformation of sample during the fracture process. WAXD results suggest that POE induces the formation of the β‐form crystalline of PP; however, DMDBS prevents the formation of it. SEM results show that the addition of DMDBS does not affect the dispersion and phase morphologies of POE particles in PP matrix. DSC and POM results show that, although POE acts as a nucleating agent for PP crystallization and which enhances the crystallization temperature of PP and decreases the spherulites size of PP slightly, DMDBS induces the enhancement of the crystallization temperature of PP and the decrease of spherulites size of PP more greatly. It is concluded that the definitely brittle–ductile transition behavior during the impact process and the great improvement of toughness of the blends are attributed to the sharp decrease of PP spherulites size and their homogeneous distribution obtained by the addition of nucleating agent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 577–588, 2008     

原位固相接枝改性碳酸钙/聚丙烯复合材料的制备

用马来酸酐（MAH）在碳酸钙（CaCO3）表面引入双键,通过原位固相接枝法将聚丙烯蜡（PPW）化学键合在CaCO3表面,制得3种接枝率的CaCO3-MAH-PPW。 将这3种改性CaCO3填充聚丙烯（PP）制备复合材料,研究了PP/CaCO3界面作用对复合材料强度的影响。 结果表明,CaCO3表面经PPW接枝改性后在PP中的分散性提高,与PP相容性变好;随着改性CaCO3表面PPW接枝率的提高,CaCO3与PP之间界面作用逐渐增强。 当PPW接枝率为4.48 mg PPW/g CaCO3时,CaCO3与PP之间的界面作用最强,复合材料拉伸强度下降最小,杨氏模量提升最大,当m(PP)∶m(CaCO3)=100∶50时,杨氏模量达0.86 GPa,是纯PP的1.63倍;而PPW化学接枝率为2.49 mg PPW/g CaCO3时,CaCO3与PP之间的界面作用适中,复合材料缺口冲击强度提升最大,且当m(PP)∶m(CaCO3)=100∶10时,缺口冲击强度达3.91 kJ/m2,是纯PP的1.35倍。     

超细CaCO_3的粒子尺寸对PP结晶行为的影响

The effects of CaCO3 on the crystallization behavior of polypropylene (PP) were studied by means of DSC and WAXD.The average sizes of the CaCO3 powders used were 0.1μm (UC) and 0.5μm (GC),respectively.The PP/CaCO3 composites at compositions of 1phr and 10 phr were investigated.The results showed that the addition of CaCO3 reduced the supercooling,the rate of nucleation and the overall rate of crystallization (except for the 10phr UC/PP sample).The crystallinity of PP was increased and the size distribution of the crystallites of α-PP was broadened.On the other hand,the crystallization rate of 10phr UC/PP is 1.5 times higher than that of neat PP.It has an overall rate of crystallization 2 times as much as that of the neat PP and has the maximum crystallinity.The sizes of crystallites and the unit cell parameters of α-PP were varied by the addition of CaCO3.β-PP was formed by addition of GC and was not detected by addition of UC.The differences of crystallization behaviors of PP might be attributed to the combined effects of the content and size of CaCO3 filled.     

Fibril formation of 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol in a polypropylene melt

Binary mixtures of 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS) within the melt of polypropylene (PP) were studied at DMDBS contents of 0.4 and 1.0 wt %. DMDBS serves as a nucleating agent in PP crystallization by formation of a nanofibrillar network. The kinetics of the DMDBS solidification process within the PP melt and the ensuing nanofibrillar structure were studied by in situ small-angle X-ray scattering (SAXS) analysis combined with imaging by electron microscopy. The dynamic lag of the fibrillar structure formation kinetics and its temperature dependence indicate a nucleation and growth mechanism, controlled by the rate of nucleation. Investigation of the fibrillar structure by electron microscopy indicates a complex structure in which long and thin fibrils (less than 100 nm in cross-section) are composed of thinner nanofibrils (less than 10 nm in cross-section).     

填充增韧聚丙烯复合材料的断裂韧性及增韧机理

用表面处理的ＣａＣＯ３填充聚丙烯（均聚物ＰＰ），ＰＰ／ＣａＣＯ３复合材料的杨氏模量和缺口冲击强度同时得到增加，克服了通常填料填充聚合物降低韧性的缺点．用Ｊ积分研究其断裂韧性给出：裂纹扩展阻力ｄＪ／ｄ（△ａ）低是聚丙烯缺口脆性的主要原因，随着填料体积分数Ｖｆ的增加ＰＰ／ＣａＣＯ３的Ｊｃ出现一极大值，但其裂纹扩展阻力却不断增大；用裂纹引发点后的Ｊｃ＝Ｊｃ＋［ｄＪ／ｄ（△ａ）］·△ａ＝Ｊｅ（Ｊ积分弹性分量）＋Ｊｐ（Ｊ积分塑性分量）可全面表征韧性聚合物材料的断裂韧性；ＰＰ／ＣａＣＯ３的Ｊｐ明显增加，是裂纹扩展阻力和Ｊｔ增加的原因．ＳＥＭ分析结出，ＣａＣＯ３填料在裂尖损伤区内引起强烈的空洞化损伤，并增强了裂尖钝化破坏过程，这些细观损伤机制的变化，导致能量耗散增加，可用滞后分量Ｊｈ定量表征．由此给出聚合物材料被增韧的Ｊ积分判据为：复合材料的Ｊｈ＞基体的Ｊｈｍ．     

Effect of Polyhedral Oligomeric Silsesquioxane and Sorbitol on Properties of Isotactic Polypropylene

Isotactic polypropylene(iPP) was modified by the introduction of polyhedral oligomeric silsesquio- xanes(POSS) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol(DMDBS). Chemical combination of (3-mercapto)- propyl-heptaisobutyl POSS with DMDBS(POSS-DMDBS), and physical mixing of DMDBS with octaisobutyl POSS (iso-POSS/DMDBS) or trisilanolisobutyl POSS(tri-POSS/DMDBS) were applied respectively to modifying iPP, and the effects of POSS and DMDBS on crystallization, rheological and mechanical properties of iPP were systematically investigated. The results indicate that iso-POSS/DMDBS and tri-POSS/DMDBS were more effective than POSS-DMDBS on the improvement of the crystallization behavior of iPP due to the higher crystallization temperature, while the crystallinity of iPP containing POSS-DMDBS was enhanced, approximately approached to that of iPP containing tri-POSS/DMDBS. The tensile strength of iPP with POSS-DMDBS was significantly increased from 34 MPa to 40 MPa, as high as that of iPP with iso-POSS/DMDBS. The different effects caused by the specific interaction between POSS and DMDBS could possibly be applied in the modification of iPP.     

CaCO3/PEEK复合体系的力学行为和热行为研究

以聚醚醚酮和碳酸钙复合体系为研究对象,考察了偶联剂和填料添加量对复合材料力学行为和热行为的影响.发现磺化聚醚醚酮作为偶联剂能有效地改善材料的力学性能,提高基体树脂的玻璃化转变温度,降低基体树脂的熔点,有助于改善聚醚醚酮的加工条件     

Nonisothermal crystallization behaviors of polypropylene with α/β nucleating agents

In this work, the nonisothermal crystallization and subsequent melting behaviors of polypropylene (PP) nucleated with different nucleating agents (NAs) have been studied. α‐phase NA 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase NA aryl amides compound (TMB‐5), and their compounds were introduced into PP matrix, respectively. The results show that the nonisothermal crystallization behaviors and crystalline structures of PP with compounded NAs are dependent on the composition of NAs. In the sample of PP with 0.1 wt % DMDBS and 0.1 wt % TMB‐5, the nucleation efficiency (NE) of TMB‐5 is much higher than that of DMDBS and PP crystallizes mainly nucleated by TMB‐5, and in this condition, β‐phase PP is the main crystallization structure. For the sample of PP with 0.2 wt % DMDBS and 0.2 wt % TMB‐5, 0.2 wt % DMDBS has higher NE than 0.2 wt % TMB5, and α‐phase is the main crystalline structure. The cooling rate is proved to be very important in controlling the nonisothermal crystallization behavior and the final crystalline structure of nucleated PP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1853–1867, 2008     

纳米CaCO_3/相容剂/PP中的界面相互作用研究

采用不同相容剂(PP-g-MAH、POE-g-MAH和EVA-g-MAH)制备了不同界面相互作用的纳米CaCO3(CC)/相容剂/PP体系,研究了相容剂/PP和相容剂/CC界面相互作用对PP/CC的结晶形态、结晶行为、熔融特性和力学性能的影响.观察到PP/CC界面相互作用提高PP结晶温度和PP/CC的模量和冲击强度,但降低了屈服强度.相容剂/CC界面相互作用进一步提高了PP/CC的结晶温度.PP/相容剂界面相互作用取决于PP与相容剂相容性.PP/PP-g-MAH相容性高有利于提高PP/CC的异相成核作用和PP/CC屈服强度和模量,但降低冲击强度.PP/POE-g-MAH部分相容对相容剂/CC界面的异相成核作用、PP/CC屈服强度和模量影响不大,可明显提高冲击强度.但PP/EVA-g-MAH不相容导致PP/CC冲击强度明显降低.     

PP/EPDM/CaCO3三元复合材料的相结构及力学性能研究

采用以化学键合方式在CaCO3表面包覆上聚丙烯蜡和将改性后的CaCO3先与EPDM复合、再与PP复合的工艺,制备PP/EPDM/CaCO3三元复合材料,以期在PP基体材料中得到EPDM包裹CaCO3的相结构.通过测量三元复合体系中各组分的表面张力,计算各可能组分对之间的界面张力和黏结功,分析三元复合体系中可能的相结构.热力学计算结果表明,三元复合体系中既存在以EPDM为壳、CaCO3为核的"核壳结构",又存在CaCO3与EPDM各自独立分散在PP基体中的结构.电镜照片进一步揭示,在PP/EPDM/改性CaCO3三元复合体系与PP/EPDM/未改性CaCO3三元复合体系中,这两种相结构的比例是不同的,在前者中以核壳结构为主.CaCO3表面性质的不同是产生这一差别的原因.由于这一结构差别的存在,PP/EPDM/改性CaCO3三元复合体系比PP/EPDM/未改性CaCO3三元复合体系具有更好的力学性能.当EPDM用量为8 phr、改性CaCO3用量为15 phr时,三元复合体系的冲击强度达14.25 kJ/m2,是纯PP的3.17倍.     

Nucleating effect of calcium stearate coated CaCO(3) nanoparticles on polypropylene

The ability of stearate coated calcium carbonate nanoparticles to promote the nucleation of polypropylene (PP) was investigated systematically. The effects of surfactant coverage and CaCO(3) particle concentration were explored using differential scanning calorimetry as well as optical and atomic microscopies. The results indicate that at the crystallization temperature of PP, a monolayer stearate coating remains as a rigid layer and provides a noticeable nucleating effect. Insufficient or excess coating diminishes the nucleating effect, the former because of the formation of agglomerates, and the latter by forming a soft layer at the PP/CaCO(3) interface at high temperatures, leading to the weak nucleating ability. Monolayer-coated nanoparticles had the strongest nucleating effect. The crystallization temperature and crystallization rate increased with the concentration of the monolayer-coated nanoparticles up to 40wt.%.     

聚丙烯多相体系中β晶的研究进展

综述了近年来聚丙烯(PP)基多相体系,如PP/弹性体(橡胶)、PP/聚乙烯(PE)、PP/对苯二甲酸乙二脂(PET)、PP/聚酰胺(PA)等共混体系和PP/CaCO3、PP/滑石粉、PP/蒙脱土(MMT)以及PP与其它无机物的复合体系中聚丙烯β晶的研究进展,阐述了在这些聚丙烯基共混和复合体系中影响聚丙烯β晶生成的因素、聚丙烯β晶的生成机理以及聚丙烯β晶对多相体系结构和性能的影响,并对富含β晶的聚丙烯(PP)基多相体系的研究和应用的发展趋势进行了展望。     

EFFECT OF PROCESSING METHOD ON THE IMPACT STRENGTH OF POM/TPU/CaCO3 TERNARY COMPOSITES

Polyoxymethylene （POM）/elastomer/filler ternary composites were prepared, in which thermoplastic polyurethane （TPU） and inorganic filler, namely, CaCO3, were used to achieve balanced mechanical properties of POM. The dispersion and phase morphology of POM/elastomer/filler composites were found to depend largely on processing method, CaCO3 content in masterbatch and the filler size. Two processing methods were employed to prepare POM/elastomer/filler ternary composites. One is called the one-step method, in which elastomer and the filler directly melt blended with POM matrix. The other is called the two-step method, in which the elastomer and the filler were mixed to get masterbatch first, which was then melt blended with pure POM of different content. The effect of phase morphology and processing method on impact strength was investigated. It was found that the two-step method results in an increase in impact strength but not for the one-step method. Additionally, the impact strength of POM ternary composites decreases with the increase in the size of CaCO3 particles.     

疏水球状碳酸钙的制备、表征及对聚丙烯力学性能的影响

以十二碳醇磷酸酯(DDP)为改性剂, 采用碳化法制备了分散性良好的球状碳酸钙粒子. 通过FESEM, XRD, FTIR及活化度和接触角测试对产物进行了表征. XRD分析结果表明, 随着DDP添加量的增加, 所得CaCO3由方解石型向文石型转变. FTIR结果表明, 改性剂与碳酸钙表面是以化学键合和物理吸附方式相结合. 当DDP含量达到2%时, 接触角为120.43°, 活化度达到99%, 碳酸钙粒子由亲水性转变为完全疏水性. 考察了反应温度和DDP含量对产物形貌与结晶行为的影响, 并对改性机理进行了初步探讨. 将产品填充到聚丙烯(PP)中, 测定了PP的力学性能.     

Preparation and properties of POSS grafted polypropylene by reactive blending

The octavinyl polyhedral oligomeric silsesquioxane (POSS) grafted polypropylene (PP) was first prepared by reactive blending. The structure and properties of physical blending and reactive blending composites of PP/POSS were investigated by wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA). WAXD analysis shows that the POSS in the reactive blending composites has better compatibility with PP than in the physical blending composites. The β-form crystalline hence disappears even the non-reactive POSS can act as an effective β-nucleating agents. DSC analysis shows the reactive blending composites have higher crystalline temperature while POSS in the physical blending composites have little effect on the crystalline temperature. The modulus of reactive blending composites increases in the presence of POSS, while that of the physical blending composites decreases with increasing POSS content.     

Effect of Organo‐Modified Nanosepiolite on Fire Behaviors and Mechanical Performance of Polypropylene Composites

The objective of the study was to investigate the effect of the organo‐modified nanosepiolite (ONSep) on improving the fire safety of polypropylene (PP). The composites based on PP, flame retardant master batch (MB‐FR, 25 wt% PP+50 wt% decabromodiphenyl ether (DBDPE)+25% antimony trioxide (ATO)) and ONSep were prepared via melt blending. The results of the limiting oxygen index (LOI) and vertical burning rating (UL‐94) test indicated that PP/40 wt% MB composites had no rating with seriously dripping phenomenon, while the LOI value was only 22.5. However, as 4 wt% ONSep was added in PP/40 wt% MB composites, the composites achieved UL94 V‐0 rating and the LOI value was 24.3. In comparison, PP/50 wt% MB composites could not reach the V‐0 rating either. The TGA results revealed that the addition of ONSep enhanced the thermal stability of the PP/MB‐FR composites. The cone calorimeter results indicated that the heat release rate, average mass loss rate, smoke production rate and smoke temperature of the PP/40 wt% MB‐FR/4 wt% ONSep composites decreased in comparison with those of PP/40 wt% MB‐FR composites. Simultaneously, the Young modulus and impact strength were also much better improved with the increase of ONSep loading. Therefore, the synergistic flame retardancy of ONSep in PP/MB‐FR matrix significantly containing a halogen based flame retardant (DBDPE) significantly improved the fire safety and mechanical properties of the composites, and allowed to decrease the total amount of brominated fire retardants.     

Effect of gamma radiation on the performance of jute fabrics-reinforced polypropylene composites

Jute fabrics-reinforced polypropylene (PP) composites (50% fiber) were prepared by compression molding. Composites were fabricated with non-irradiated jute fabrics/non-irradiated PP (C-0), non-irradiated jute fabrics/irradiated PP (C-1), irradiated jute fabrics/non-irradiated PP (C-2) and irradiated jute fabrics/irradiated PP (C-3). It was found that C-3 composite performed the best mechanical properties over other composites. Total radiation dose varied from 250–1000 krad and composites made of using 500 krad showed the best results. The optimized values (C-3 composites) for tensile strength (TS), bending strength (BS) and impact strength (IS) were found to be 63 MPa, 73 MPa and 2.93 kJ/m², respectively.     

磨盘碾磨制备PP/石墨复合粉末的研究

通过磨盘碾磨制备了PP 石墨复合粉末 ,用粒度分析、SEM和XRD表征了复合粉末的形貌特征、结构与性能 .结果表明 ,磨盘碾磨实现了PP与石墨的粉碎、分散和混合 ,经过 2 5遍碾磨 ,石墨与PP已互相嵌入 ,均匀分散 ;PP 石墨复合粉末具有不规则薄片状形貌特征 ;XRD表明 ,磨盘碾磨使PP和石墨的结晶度降低 ,晶面间距增大 ,晶粒尺寸减小 .PP 石墨复合粉末与聚丙烯共混复合可制备出具有良好抗静电性能的复合材料 .     

PP-g-(MAH/St)和PP-g-MAH对聚丙烯/木粉复合材料性能的影响

在转矩流变仪中用熔融接枝法制备马来酸酐(MAH)和苯乙烯(St)接枝聚丙烯（PP）-PP-g-(MAH/St)和PP-g-MAH,将其作为聚丙烯/木粉复合材料的相容剂。 FTIR证实MAH和St单体与PP发生接枝反应。 用SEM和DSC等手段考察两种相容剂对PP/木粉复合材料微观形貌和结晶性能的影响,探索了各种PP/木粉复合材料加工和力学性能不同的内在原因。 SEM显示,PP-g-(MAH/St)改性木粉比PP-g-MAH改性木粉在PP基体中分散性更佳,木粉与PP的界面更加模糊,相容性进一步改善。 DSC结果表明,PP-g-(MAH/St)改性体系可增强木粉对PP的异相成核作用,提高结晶温度和结晶度。 复合材料的加工和力学性能测试结果表明,PP-g-(MAH/St)改性效果明显优于PP-g-MAH。 复合材料的熔体质量流动速率随相容剂用量的增加而逐步下降,PP-g-(MAH/St)改性体系拉伸强度和弯曲强度却逐步上升,并在相容剂用量为4.8 g/100 g PP时达到极值。 此时其拉伸强度达40.62 MPa,分别是未改性体系和PP-g-MAH改性体系的1.29和1.17倍;其弯曲强度达45.72 MPa,分别是未改性体系和PP-g-MAH改性体系的1.23和1.59倍;而无缺口冲击强度却在相容剂用量为3.6 g/100 g PP时达到极值13.35 kJ/m2,分别是未改性体系和PP-g-MAH改性体系的1.62倍和1.42倍。