Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

Effect of filler treatments on rheological behavior of calcium carbonate and talc‐filled polypropylene hybrid composites

Commercial stearic acid treated calcium carbonate (CaCO₃) was used to make a comparative study on rheological behavior of the CaCO₃ and talc‐filled polypropylene (PP) hybrid composites with nontreated filler. Apparent shear viscosity and extrudate swell were investigated with variation of filler ratio and temperature with 30% by weight total of filler was used in PP composite. The Shimadzu capillary rheometer was used to evaluate shear viscosity and shear rate of the composite. It was found that the shear viscosities decrease with increasing shear rate. The apparent shear viscosity of the composite containing the stearic acid treated is slightly lower than untreated filler. Shear thickening behavior at higher shear rate has also shown by 15/15 treated composites at higher temperature about 220°C and investigation by SEM has proved that filler being densely packed at that condition. Treated composites also exhibit lower swelling ratio value than untreated composite, and swelling ratio also decreases linearly with increasing temperature and the die length–diameter ratio. It is believed that dispersion of filler play an important role not only on shear viscosity but also on swelling ratio of PP composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5421–5426, 2006     

Structure‐properties relationship in resol/montmorillonite nanocomposites

Polymer/layered silicate nanocomposites were prepared, adding modified, and nonmodified montmorillonites to a resol resin. It was observed that the composites exhibited an intercalated disordered structure by means of X‐ray diffraction (XRD) and transmission electronic microscopy. The crosslinking density of the resol network was greatly influenced by the presence and type of clay that was added to the resin. The composites filled with the modified montmorillonites showed a lower glass transition temperature value as well as a higher degradation peak at ～ 400°C, which is characteristic of the degradation of methylene bridges, indicating a decrease in the crosslinking density of the resol network when modified clays are added. Resol/unmodified montmorillonite composites exhibited different behavior comparing to the other composites and the resol. A higher thermal resistance was observed in the fragmentation zone and a different tan δ response was seen in the DMA analysis. These differences in the behavior of the composites could be because of the interaction between the resol prepolymer and the clay modifiers and as a result of their chemical compatibility. The hardness and elastic modulus of the resol were improved with the addition of clays. However, higher values were obtained for the composite made with the more dispersed montmorillonite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study of biodegradable polylactide/poly(butylene carbonate) blend

Polylactide (PLA) was melt blended with poly(butylene carbonate) (PBC) in an effort to improve the toughness of the PLA without compromising its biodegradability and biocompatibility. The miscibility, morphology, thermal behavior, and mechanical properties of the blends were investigated. The blend was an immiscible two‐phase system with PBC uniformly dispersed within the PLA matrix. Because of the interfacial function, the incorporation of PBC accelerated the crystallization rate of PLA. By the incorporation of PBC, a polylatide‐based material with high stiffness and toughness was achieved. Even at 10% of PBC, high elongation at break of 139% was obtained, while the tensile strength remained as high as 50.7 MPa. The Pukanszky model gave credit to modest interfacial adhesion between PLA and PBC although PLA/PBC is an immscible blend. The plastic deformation, occurring via debonding process, is an important energy‐dissipation process and leads to a toughened, biodegradable polymer blend. The important point is that the toughening mechanism requires only modest level of adhesion between particles and the polymer. The molecular mobility is a crucial factor for yield stress and plastic flow. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure development and property changes in high‐density polyethylene/calcium carbonate blends during pan‐milling

A new self‐designed mechanochemical reactor, inlaid pan‐mill, was used in studying high density polyethylene (HDPE) and calcium carbonate (CaCO₃) blends. The effects of CaCO₃ on the crushing and structure of HDPE matrix and the properties of HDPE/CaCO₃ blends were investigated. Scanning electron microscopy, Fourier transformed IR spectroscopy, dynamical mechanical testing analysis, capillary rheometer, and Instron material testing system were used to characterize the structure of HDPE and evaluate the properties of HDPE/CaCO₃ blends. The introduction of calcium carbonate during milling improved milling efficiency, and time needed for each cycle was greatly reduced. Oxygen‐containing groups on HDPE chains, which were produced during milling, increased interfacial interactions and improved the dispersion and distribution of calcium carbonate particles in HDPE/CaCO₃ blends. Rheological, thermal, and mechanical properties were also improved. The elongation at break of milled blends with high concentrations of calcium carbonate was significantly higher than that of unmilled blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1459–1464, 1999     

Basalt fiber reinforced and elastomer toughened polylactide composites: Mechanical properties,rheology, crystallization,and morphology

A series of the reinforced and toughened polylactide (PLA) composites with different content of basalt fibers (BF) were prepared by twin screw extruder. The toughness of BF/PLA composite s was improved further by the addition of polyoxyethylene grafted with maleic anhydride (POE-g-MAH), ethylene–propylene–diene rubber grafted with maleic anhydride (EPDM-g-MAH), and ethylene-acrylate-glycidyl methacrylate copolymer (EAGMA), relatively. The mechanical properties, rheology, crystallization, and morphology of BF/PLA composites were studied. The results showed that basalt fiber had significant reinforcing and toughening effect in comparsion with glass fiber. EAGMA was more effective in toughening BF/PLA composites than POE-g-MAH and EPDM-g-MAH. When the content of EAGMA achieved to 20 wt %, the impact strength of BF/PLA/EAGMA composite increased to 33.7 KJ/m², meanwhile the value was improved by 71.1% compared with pure PLA. According to dynamic rheometer testing, the use of the three kinds of elastomers increased the melt dynamic viscosity. Differential scanning calorimetry analysis showed that POE-g-MAH and EPDM-g-MAH can decrease the cold crystallization temperature (T_cc) to approximately 20°C and dramatically improve crystallinity (χ_c) of BF/PLA composites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Foaming behavior of microcellular foam polypropylene/modified nano calcium carbonate composites

A new process was used to prepare microcellular foams with supercritical carbon dioxide as the physical foaming agent in a batch. The foaming temperature range of the new process was about five times broader than that of the conventional one. Characterization of the cellular structure of the original polypropylene (PP) and PP/nano‐CaCO₃ (nanocomposites) foams was conducted to reveal the effects of the blend composition and processing conditions. The results show that the cellular structure of the PP foams was more sensitive to the foaming temperature and saturation pressure variations than that of the nanocomposite foams. Uniform cells of PP foams are achieved only at a temperature of 154°C. Also, the low pressure of 20 MPa led to very small cells and a low cell density. The competition between the cell growth and cell nucleation played important role in the foam density and was directly related to the foaming temperature. Decreasing the infiltration temperature depressed the initial foaming temperature, and this resulted in significantly larger cells and a lower cell density. A short foaming time led to a skin–core structure; this indicated that a decrease in the cell size was found from skin to core, but the skin–core structure gradually disappeared with increasing foaming time. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of microstructures on the viscoelastic and rheological properties of metallocene‐catalyzed cyclo‐olefin copolymers: A preliminary study

We characterized metallocene‐catalyzed cyclo‐olefin copolymers (mCOCs) with similar heat distortion temperatures but dramatic differences in melt‐flow indices to understand how the molecular conformation affected their rheological and viscoelastic properties. The mCOC conformations were identified with ¹³C‐NMR, whereas the viscoelastic and rheological properties were measured with cone‐and‐plate and high‐pressure capillary rheometers. Our preliminary results showed that the mCOC rheological and viscoelastic properties might depend strongly on the conformation rather than the norbornene content, molecular weight, and molecular weight distribution. mCOCs containing ‐NNN‐ locks (where N represents norbornene) exhibited stronger molecular entanglements than those having no ‐NNN‐ blocks, as reflected in lower crossover frequencies and higher crossover torque. Furthermore, the existence of larger rigid ‐NNN‐ blocks resulted in higher molten viscosities and flow activation energies. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3695–3701, 2002     

Fractal analysis of polypropylene composite filled with nano‐calcium carbonate

Polypropylene (PP) and nano‐calcium carbonate (CaCO₃) composites were prepared by melt mixing in a corotating twin‐screw extruder. Transmission electron microscopy study and particle size analysis revealed the dispersion and the size distribution of CaCO₃ in PP. With the increase of loading of filler, CaCO₃ nanoparticles densely aggregated together and the dispersion of filler became bad. The fractal dimensions of the composites were determined using fractal concept. The fractal dimensions of D and D_k described the irregularities of the shape of an object and the distributions of particle populations, respectively. The D and D_k values were influenced by the content of filler, i.e., the D values increased, and the D_k values decreased with the increase of loading of filler. When the loading of filler was low, the values of D and D_k of PP composites differ slightly than the counterparts of PP/PP‐g‐MA (50 wt %) blend. For 20 wt %, they were almost identical. This fact showed that the fractal dimension was correlated with the dispersion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

由氯化钙制备纳米碳酸钙研究

随着国民经济的发展,对纳米碳酸钙的需求量越来越大.基于化工生产中大量副产氯化钙,以氯化钙和碳酸铵为原料,对制备纳米碳酸钙进行了研究.实验研究了添加剂、反应温度和反应物浓度等工艺条件对产物粒径的影响,并采用XRD和TEM对产物进行了初步分析.实验结果表明:不同的添加剂对产物粒径以及形貌具有一定的影响,当氯化钙和碳酸铵配料比为1.0:1.0 mol/mol、反应温度为15℃和氯化钙浓度为0.3 mol/L时,以有机醇A和磷酸系化合物G为添加剂制备的产物为方解石型球状碳酸钙,粒径在50 nm左右.     

纳米碳酸钙丁腈橡胶母炼胶的制备及性能评价

采用乳液法制备了丁腈橡胶（NBR）/纳米碳酸钙（NCC）共沉橡胶,并对其性能进行了评价。基本性能实验结果表明：与NBR相比,共沉胶焦烧时间略有降低,正硫化时间略有增加,最大扭矩明显提高,共沉胶具有优异的基本物理性能;工业配方配合显示：共沉胶具有优异的基本物理性能、耐热空气老化性能以及耐热油性能;共沉胶成本明显降低,具有良好的应用前景。     

Structure–property relationship in PP/LDPE blend composites: The role of nanoclay localization

This article reports, for the first time, on how the kinetics and thermodynamics of the melt‐processing control the nano/micro‐structure development and properties of nanoclay‐filled polypropylene (PP)/low‐density polyethylene (LDPE) blend ternary composites. Morphological characterization suggests that the nano/micro‐structure of the PP/LDPE (80/20) blend can be controlled by incorporating nanoclay alone or by adding a mixture of organoclay and maleated compatibilizers. Simultaneous mixing of PP, LDPE, maleated compatibilizers, and organoclay results in homogeneous distribution of intercalated silicate layers in all the phases of the blend, a feature which profoundly affects the thermal stability and tensile and rheological properties of the blend composites. For example, the elongation‐at‐break for PP increases from 28.1 to 155.6% for composite containing both organoclay and maleated compatibilizers, whereas the thermal stability for PP increases from 269.8 to 303.3 °C for the same composite. However, the impact strength of the PP/LDPE blend decreases with incorporation of organoclay, regardless of the phase in which the nanoclay particles are localized. In summary, the obtained results show that regardless of the phase in which the nanoclay is localized, the morphology, and hence the properties, of the ternary composites are superior to those of the neat blend. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46193.     

Toughening of polylactide with epoxy‐functionalized methyl methacrylate–butadiene copolymer

Glycidyl methacrylate‐functionalized methyl methacrylate–butadiene (MB‐g‐GMA) copolymers were prepared via an emulsion polymerization process. These functionalized copolymers were blended with polylactide (PLA). Dynamic mechanical analysis and differential scanning calorimetry results showed that the addition of MB‐g‐GMA did not result in a marked change in the glass transition temperature of PLA. With an increase of MB‐g‐GMA content, the tensile strength of the blends decreased; however, the elongation at break and impact strength increased significantly. From scanning electron micrographs, there was large plastic deformation (shear yielding) in blends subjected to impact tests, which was an important energy‐dissipation process and led to a toughened polymer. Rheological investigation demonstrated that there was a significant dependence of viscosity on composition. When the MB‐g‐GMA content increased, the viscosity began to increase. © 2013 Society of Chemical Industry     

碳酸钙在塑料中应用进展

碳酸钙是塑料加工时使用的最重要的无机粉体添加剂之一.综述了碳酸钙在塑料中的重要作用;介绍了塑料加工对碳酸钙的基本要求(价格、白度、粒度及分布等);研究了碳酸钙的表面处理问题并且介绍了几种表面处理剂和表面处理设备;重点研究了纳米碳酸钙在塑料中的应用及在基体中的分散问题;最后以碳酸钙增韧高密度聚乙烯(HDPE)专用料、光钙型降解塑料等为例介绍了碳酸钙在塑料加工行业中的应用进展.     

碳酸钙产品分类与命名建议

碳酸钙产品广泛应用于塑料、造纸、涂料、橡胶、日化、医药、食品、饲料等行业.根据加工方法不同可分为重质碳酸钙(GCC)、轻质碳酸钙(PCC);根据是否改性可分为普通碳酸钙和活性碳酸钙;根据用途不同可分为专用碳酸钙.为了方便行业管理,便于统计,有利于用户选用,建议按产品加工方法及其平均粒径大小分为轻质和重质两大类.轻质碳酸钙分为轻质碳酸钙(＞2.0μm)、超细碳酸钙(0.1～2.0μm)、纳米级碳酸钙(≤0.1μm )等3个级别,每个级别中分为活性与普通产品、各种专用产品等;重质碳酸钙分为重质碳酸钙(＞10μm)、微细重质碳酸钙(2.0～10μm)、超细重质碳酸钙(0.1～2.0μm)等3个级别,每个级别中分为活性与普通产品、各种专用产品等.各类各种碳酸钙产品物理及化学指标分别符合国家、行业或企业标准要求.     

快速测定碳酸锶中的钙含量的研究

利用硝酸锶、硝酸钡、硝酸钙在有机溶剂中溶解度的不同,把碳酸盐样品转化为硝酸盐,再用不同有机溶剂洗涤其中的硝酸钙,用EDTA滴定样品中钙的含量。考察了不同有机洗涤溶剂、洗涤次数对碳酸锶中钙含量测定的影响,并作回收率实验。建立了快速、准确,适用于碳酸锶生产过程中钙含量的快速分析的方法：用无水乙醇-无水乙醚（体积比为1∶1）混合液作洗涤液,洗涤次数为4次,该方法的回收率为98.4%~100.5%、RSD为0.02%。     

世界碳酸钙工业发展近况

世界碳酸钙工业发展迅速，产能不断增加，首先介绍了近几年来重质研磨碳酸钙（GCC）产业的发展概况，重点介绍了中国、日本、马来西亚、韩国、泰国的GCC产业及国际著名GCC生产公司在中国的经营情况。其次介绍了世界轻质沉淀碳酸钙（PCC）的市场概况及国外大型PCC生产公司的基本情况。最后，重点介绍了中国大陆地区的碳酸钙生产与市场情况，并通过分析近几年中国碳酸钙产品的进出口数量及价格情况指出，开发适合碳酸钙用户需求的新产品、新技术，参与国际竞争是今后中国碳酸钙生产企业的发展方向。     

Rheological behavior and mechanical properties of sawdust/polyethylene composites

We have characterized the melt rheological behavior and the solid tensile properties of sawdust/polyethylene composites prepared in an internal mixer. Various concentrations (from 0 to 60 wt %) and three particle sizes have been tested, in presence of a coupling agent (maleic anhydride grafted polyethylene). In the molten state, for each particle size, a mastercurve of the complex viscosity as function of frequency can be plotted, using a shift factor depending on weight fraction. We show that the shift factors can be described by a Krieger‐Dougherty law, leading to a “universal” viscosity law of the Carreau‐Yasuda type. In the solid state, the presence of sawdust increases Young modulus in uniaxial elongation, mainly for small size particles, but reduces dramatically deformation at break and tensile strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

碳酸钙晶型的肉豆蔻酸调控研究

采用硝酸钙和碳酸钠的复分解反应制备碳酸钙,通过加入肉豆蔻酸对碳酸钙的晶体结构和表面性质进行调控,采用SEM、XRD、FT-IR、TG和XPS等方法研究了添加肉豆蔻酸对碳酸钙晶体结构的影响。结果表明,加入肉豆蔻酸之后,碳酸钙的晶体结构由球霰石变成方解石,形貌由球形变成了不规则的长方体形;碳酸钙的表面全部被活化,由亲水性变成疏水性,表面疏水后,碳酸钙的团聚程度明显降低;肉豆蔻酸的羧基阴离子和钙离子发生了化学结合反应,增强了碳酸钙结构的稳定性。总之,肉豆蔻酸的加入为碳酸钙的晶型调控与表面改性提供了一条简单的思路。