Microstructure and fracture behavior of polypropylene/barium sulfate composites

The microstructure, mechanical properties, and fracture behavior of polypropylene (PP)/barium sulfate (BaSO₄) composites were studied. Four composite samples with different PP‐BaSO₄ interface were prepared by treating the filler with different modifiers. The fracture behavior of the composites under different strain rates was studied by means of Charpy impact tests and essential work of fracture (EWF) tests. It is shown that a moderate interfacial adhesion is favorable for toughening, which ensures that the particles transfer the stress and stabilizes the cracks at the primary stage of the deformation, and satisfies the stress conditions of plastic deformation for matrix ligaments subsequently via debonding. Very strong interfacial adhesion is not favorable for toughness, especially under high strain rate, because the debonding‐cavitation process may be delayed and the plastic deformation of matrix may be restrained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1207–1213, 2006     

Crystallization and melting behaviour of polypropylene ‘catalloys’

The crystallization and melting behaviour of polypropylene ‘catalloys’ (PP‐cats) as well as pure polypropylene (PP) were investigated using differential scanning calorimetry. The results showed that, for PP‐cats and PP, a single melting peak of PP appeared under slow cooling rate. When the cooling rate is fast enough in the non‐isothermal case, or the crystallization temperature is relatively high in the isothermal case, a shoulder peak appears in front of the melting peak with increasing ethylene content in PP‐cats. It is believed that this shoulder is induced by recrystallization of crystals initially formed during non‐isothermal or isothermal crystallization. When the ethylene component in PP‐cats reached a certain level, there existed a melting peak of polyethylene (PE) crystallized during the cooling process. Polarized optical microscopy (POM) showed that the spherulites formed by PP‐cats were much smaller and had less perfect morphology compared with that formed by pure PP at the same cooling rate. And with the increase of the cooling rate, the spherulites could not be clearly observed. Copyright © 2004 Society of Chemical Industry     

Crystallization and melting behavior in syndiotactic polypropylene: Origin of multiple melting phenomenon

The melting behavior of syndiotactic polypropylene (s‐PP) after isothermal crystallization from the melt state was studied using differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) techniques. Three melting endotherms were observed for isothermal crystallization at high degrees of undercooling. The minor endotherm, located closed to the corresponding crystallization temperature, was postulated to be the melting of the secondary crystallites formed at the crystallization temperature. The low‐temperature melting peak was found to be the melting of the primary crystallites formed, and the high‐temperature melting peak was a result of the melting of the crystallites recrystallized during a heating scan. The triple‐melting behavior observed in subsequent melting endotherms of s‐PP was therefore described as contributions from melting of the secondary crystallites and their recrystallization, partial melting of the less stable fraction of the primary crystallites and their recrystallization, melting of the primary crystallites, and remelting of the recrystallized crystallites formed during the heating scan. In addition, determination of the equilibrium melting temperature for this s‐PP resin according to the linear and nonlinear Hoffman–Weeks extrapolations provided values of 143.1 and 185.6°C, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1083–1097, 2001     

Crystallization and melting of highly filled polypropylene composites prepared with surface‐treated fillers

Polypropylene (PP) composites with high filler content have been prepared with surface‐treated fillers. The effect of the filler is twofold; nucleation of crystallization occurs, though the PP is also adsorbed onto the filler thereby retarding its motion. Differential scanning calorimetry has been used to study the crystallization of the PP. Melting and recrystallization during melting has been characterized by differential scanning calorimetry. The properties of the composites are more than an additive combination of the filler and polymer. In the case of highly filled composites, the morphology of the PP is important in limiting brittleness and for the strength of the interface between filler and polymer. Surface treatment of the filler has been found to have a significant control over the morphology and properties of the composites. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1942–1948, 2001     

原位形成FPP偶联Al(OH)3/PP中的界面相互作用研究

制备低含量Al(OH)3填充PP复合材料[Al(OH)3/PP]，研究原位形成的官能团化聚丙烯（FPP）在Al(OH)3/PP中的结晶、熔融行为，结晶形态，以及与各组分间的相互作用。研究认为，在复合材料中存在Al(OH)3与FPP间的化学作用，FPP与PP的相容与共结晶作用，Al(OH)3表面异相诱导成核作用，FPP对Al(OH)3表面异相诱导成核作用的活化作用等，从而改善了Al(OH)3/PP的物理与力学性能。     

Isothermal melt crystallization and melting behaviour of syndiotactic polypropylene

The lamellar morphological information and subsequent melting behaviour of syndiotactic polypropylene (s‐PP) samples isothermally crystallized at crystallization temperatures ranging from 30 to 95 °C have been investigated using a combination of wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS) and differential scanning calorimetry (DSC) techniques. Three known methods for determining the equilibrium melting temperature T_m°, namely the Gibbs–Thomson extrapolation, the linear Hoffman–Weeks extrapolation and the non‐linear Hoffman–Weeks extrapolation, have been employed to evaluate this important thermodynamic parameter, and the results obtained are compared. Finally, an estimate of the equilibrium melting temperature for a perfect s‐PP sample (T_m°)_100% is given. © 2000 Society of Chemical Industry     

Interfacial interaction in AI(OH)3/polypropylene composites modified by insitu‐functionalized polypropylene

To investigate the interfacial interaction of AI(OH)₃/polypropylene (PP) composites modified by in situ‐functionalized polypropylene (FPP), AI(OH)₃/polypropylene (PP) composites containing a low AI(OH)₃ content, modified by in situ‐grafted acrylic acid, were prepared by a one‐step melt‐extrusion process. The effect of in situ FPP on the crystallization and melting behavior, crystalline morphology of the composites, and interfacial interaction between the filler and PP was investigated. The crystallization and melting behavior and crystalline morphology of PP in the composites depended upon the interfacial physical [heterogeneous nucleation of AI(OH)₃; cocrystallization and compabilitization of PP with in situ FPP] and the interfacial chemical interaction between both the components in the composites. FTIR results indicated that there exists a chemical reaction between AI(OH)₃ and in situ FPP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 110–120, 2002; DOI 10.1002/app.10270     

Crystallization and melting behaviour of photodegraded polypropylene — II. Re-crystallization of degraded molecules

Isotactic polypropylene bars were exposed to ultraviolet radiation (UV) in the laboratory for periods up to 48 weeks causing a reduction in molecular size and the build-up of chemical groups like carbonyls and hydroperoxides. The specimens were re-crystallized from the melt under isothermal and non-isothermal conditions and investigations were conducted by differential scanning calorimetry (DSC), X-ray diffraction, and light microscopy. At first the fractional crystallinity of the re-crystallized materials increased with exposure as the result of decreasing molecular size, but for longer exposures the fractional crystallinity decreased because of the increase in concentration of chemical impurities. In highly degraded specimens, the presence of γ-phase crystals was detected. Kinetic studies revealed that the rates of nucleation and growth may be affected differently by photodegradation, and that the degraded molecules crystallized much faster than the unexposed material when their rates of crystallization under the same supercooling are compared. Double melting peaks were observed in DSC thermograms and were shown to be due to re-organization during heating, but in some cases the segregation of highly defective molecules is the major reason for peak doubling. Molecular segregation also changes the spherulite morphology during crystallization, as revealed by polarized light microscopy. © 1997 Elsevier Science Ltd.     

沉淀硫酸钡粉体流动性及影响因素分析

以芒硝-硫化钡法工业化生产的沉淀硫酸钡为对象,在对普钡、超细钡和精细钡粉体的流动性指数进行测试的基础上,分析了影响沉淀硫酸钡粉体流动性能的主要因素,并着重分析了沉淀硫酸钡粉体受压缩时颗粒间范德华力的变化对流动性的影响,得出了内聚力以压缩率的平方递增的关系。     

离子交换法合成硫酸钡的研究

碳酸钡与硫酸钾为原料,采用离子交换法合成硫酸钡,考察了工艺参数对硫酸钡产率的影响,并采用X射线衍射（XRD）、扫描电子显微镜（SEM）、傅里叶变换红外光谱（FTIR）等分析方法对产物晶相、形貌做了表征。结果表明：在c（SO₄ ^2-）=0.007 5 mol/L、液固质量比（g/g）为800∶1、反应温度为30 ℃、反应时间为72 h的最优条件下,硫酸钡的产率最高可达98.25%,得到的硫酸钡为规则的片状,结晶良好,纯度较高。     

聚丙烯基复合材料的结晶行为

综述了3类聚丙烯(PP)基复合材料体系包括PP/无机物体系、PP/有机物体系和PP／聚合物体系的结晶行为。阐述了PP基体的结晶结构以及结晶动力学特征,包括添加物对PP的结晶温度、结晶速率及结晶度等的影响;分析了结晶行为对复合材料力学性能的影响。复合材料界面对基体聚合物取向结晶形态及结晶行为的影响等还需进一步研究。     

Influence of syndiotacticity and annealing temperature on the double melting peak behaviour of syndiotactic polypropylene

Fractionated syndiotactic polypropylene (sPP) samples with homogeneous tacticity were annealed at different temperatures. The influence of syndiotacticity and annealing temperature on the double melting peak phenomena were investigated. It is found that all fractions show double melting peaks at 75°C annealing temperature, while the low peak disappears when the fractions with higher syndiotacticity are annealed at 85°C and above. The fraction with the lowest syndiotacticity remains the same at any annealing temperature. In combination with wide-angle X-ray diffraction experiments, the double peaks are believed to correspond to the melting of cell II and III. The results indicate that higher temperature and syndiotacticity are the external conditions and internal structural factor that permit cell II to transform into cell III. © 1999 Society of Chemical Industry     

Crystallization and melt behavior of Mg(OH)2/PP composites modified by functionalized polypropylene

The crystallization and melting behavior of Mg(OH)₂/PP composites modified by the addition of functionalized polypropylene (FPP) or acrylic acid (AA) and the formation of in situ FPP were investigated by DSC. The results indicated that addition of FPP increased the crystallization temperatures of PP because of the nucleation effect of FPP. The formation of in situ FPP resulted in a reduced crystallization rate, melting point, and degree of crystallization attributed to the decreased regularity of the PP chain. For Mg(OH)₂/PP composites, the addition of Mg(OH)₂ increased the crystallization temperatures of PP resulting from a heterogeneous nucleation effect of Mg(OH)₂. The addition of FPP into Mg(OH)₂/PP composites further enhanced the crystallization temperatures of PP. It is suggested that there is an activation of FPP to the heterogeneous nucleation effect on the Mg(OH)₂ surface. The addition of AA also increased the crystallization temperatures of PP in Mg(OH)₂/PP composites, although the crystallization temperature of PP was not influenced by the AA content, which is explained by the heterogeneous nucleation effect of the Mg(OH)₂ surface activated by FPP and AA. A synergistic effect on the crystallization of PP in Mg(OH)₂/PP composites further increased the crystallization temperatures of PP. However, The crystallization temperatures of Mg(OH)₂/PP composites modified by in situ FPP were lower than those of Mg(OH)₂/PP composites modified by addition of either FPP or AA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3610–3621, 2004     

硫酸钡废水的综合治理

以硫酸钡生产中产生的废水为原料,采用双效蒸发、浓缩工艺制取硫化钠。最佳工艺控制条件:废水中硫化钠质量分数4%左右,一效蒸发器料液终点硫化钠质量浓度70g/L,二效蒸发器料液终点密度1. 14 ~1. 24g/mL,二效蒸发器终点料液充分澄清后,浓缩至硫化钠质量分数60%,包装即为固体硫化钠,经制片机制片后即为片状硫化钠。该方法技术可行,解决了废水对环境的污染。     

Crystallization behaviors in the isotactic polypropylene/graphene composites

Crystallization behaviors and kinetics of iPP in an in-situ prepared isotactic polypropylene/graphene (iPP/G) composites were studied in this paper. In samples used in this study, the graphene fillers were well dispersed, and the interfacial adhesion exhibited enhanced features between graphene and iPP components. The thermal stability of the composites was improved by about 100 °C compared to the pristine iPP. It was found that the crystallization morphology, crystallization rate and kinetics of the iPP/G composites were significantly influenced by the presence of graphene. The nucleation and epitaxial growth of iPP on the graphene surface were observed and studied in detail. It was observed that the nucleation of iPP favored to occur at the wrinkles and edges due to the good match of the lattice parameters and the weak spatial hindrance compared to the smooth surface. Numerous nuclei epitaxially formed and the size of the crystals was very small. The schematic diagram was also proposed for the nucleation and growth process of iPP on the graphene surface in the iPP/G composites. Meanwhile, the overall crystallization kinetics and crystals growth were analyzed through Avrami equation. The obtained Avrami index n decreased with the graphene loadings and was close to 2 for the iPP/G composites, which implied that the growth of iPP in the composites was in two-dimension. And this was caused by the structure of graphene and the spatial confinement effect of graphene platelets in the iPP/G composites.     

Formation and behaviour of low‐temperature melting peak of quenched and annealed isotactic polypropylene

The process of low‐melting point (LMP) α‐phase formation in a quenched and annealed isotactic polypropylene (iPP) was studied by means of differential scanning calorimetry. The influence of preparation conditions (quenching and annealing temperatures, annealing times and sample thickness), together with the measurement parameters (heating and cooling rates), on the iPP melting behaviour are analysed. The results reveal a constant yield of LMP crystals over a wide range of quenching temperatures. This study also suggests that the LMP α‐crystals originate from the crystallization of polymer portions, which are somewhere between the amorphous and the smectic phase on the macromolecular scale of order. © 2001 Society of Chemical Industry     

超细硫酸钡化合反应研究

比较了制备超细硫酸钡的两种化合工艺，选择了较易实现的剧烈搅拌法，确定了最佳工艺条件为：间歇反应，在NaSO4溶液和BaS溶液的浓度分别为1．000mol/L和0．5000mol/L、温度为40℃、在300r/min搅拌速度下快速将Na2SO4溶液加入BaS溶液中并连续搅拌1min，所得BaSO4颗粒粒径小、耗能少。探讨了连续化实验方案。     

沉淀硫酸钡生产工艺技术改造

针对传统沉淀硫酸钡生产工艺存在的问题，如：重晶石利用率低、系统热利用率低、产品品质低、工艺装备老化、产品品种单一等，对传统沉淀硫酸钡生产工艺实施了全过程的技术改造，使产品品质得以提高，运行成本明显降低，实现了工艺系统按照产品结构功能化的优化配置。     

纳米硫酸钡的湿法改性研究

采用高剪切混合乳化机替代普通搅拌器,湿法反应改性纳米硫酸钡,考察了乳化时间、乳化温度、改性剂用量、纳米硫酸钡悬浮液固含量对改性后纳米硫酸钡活化度的影响。采用红外光谱仪、热重分析仪和扫描电子显微镜对改性后纳米硫酸钡的包覆情况、形貌做了表征。实验结果表明,采用高剪切混合乳化机湿法反应改性纳米硫酸钡,在乳化时间为15 min、乳化温度为65 ℃、改性剂用量为5%（质量分数）、悬浮液固体质量浓度为100 g/L的条件下,可以得到活化度为99.88%、吸油值为0.497 5 g/g的粉末状疏水性纳米硫酸钡。