Nonisothermal crystallization kinetics of polypropylene composites reinforced with down feather fiber

Nonisothermal crystallization kinetics of pure polypropylene and polypropylene/down feather fiber composites were investigated using a differential scanning calorimeter at five different cooling rates. The experimental data on crystallinity versus temperature were analyzed by Avrami, Ozawa, and Liu models, respectively. The results indicated that the presence of down feather fiber served as nucleating agent and increased the onset and peak temperatures of crystallization of polypropylene/down feather fiber composites. Interestingly, polypropylene/down feather fiber composites showed a slower primary crystallization and a faster secondary crystallization than pure PP, meaning that down feather fiber retired the crystallizaiton process of PP matrix. The nucleation activity and activation energies were also calculated and agreed well with these results. Wide‐Angle X‐ray diffraction patterns indicated that down feather fiber induced the formation of β‐monoclinic crystals in polypropylene matrix. These phenomena were definitely different from the nonisothermal crystallization kinetics of polypropylene composite based on inorganic particles and organic cellulose fibers. POLYM. COMPOS., 37:3103–3112, 2016. © 2015 Society of Plastics Engineers     

Isothermal crystallization of metallocene‐based polypropylenes with different isotacticity and regioregularity

Three polypropylenes with various isotacticities and regioregularities were prepared with metallocene catalysts at different polymerization temperatures. WAXD results showed that the relative content of γ crystals in polypropylenes increased as isotacticity decreased. It was found that the γ crystal overcame the α crystal and became predominant in polypropylene of low isotacticity and high regioerrors. More γ crystals were also formed at higher crystallization temperatures. The isothermal crystallization kinetics of α and γ crystals were compared and the metastability of these two crystal phases was interpreted in terms of the crystallization kinetics. It was observed that the α crystal has a faster crystallization rate than that of the γ crystal and, thus, higher stability at low temperature. By contrast, the γ crystal tends to have a faster crystallization rate and becomes more stable at high temperature. The metallocene‐based polypropylenes with different isotacticities have similar Avrami exponents. As the content of the γ crystal increases, double melting peaks become more evident. Equilibrium melting temperatures were derived from Hoffman–Weeks analysis and very close equilibrium melting temperatures were obtained, 185.5 and 184.0°C, for two metallocene‐based polypropylenes containing major α crystals and one of 182.5°C for the polypropylene with predominant γ crystals. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3215–3221, 2003     

Studies on simultaneous crystallization of polypropylene/nylon 12 blends

The effect of the morphology of polypropylene (PP)/nylon 12 (PA12) blends on their crystallization behaviour is studied using differential scanning calorimetry and scanning electron microscopy. In PP/ maleated polypropylene (PP-MA)/PA12=65/10/25 blend, simultaneous phase (PA12) is smaller than 0.5 μm, PP crystallizes first and its crystals induce the crystallization of PA12. When some of the PA12 particles are larger than 0.5 μm, this part of PA12 crystallizes first. Then this part of the PA12 crystals induces the crystallization of PP, and PP crystals induced the crystallization of PA12 fine droplets in turn.     

The effects of alkaline earth dehydroabietate on the crystallization process of polypropylene

In this article, the influence of alkaline earth dehydroabietates, which were prepared from Na‐dehydroabietate, on crystallization of polypropylene (PP) from the melt state was studied by differential scanning calorimetry and polarization microscopy. It was found that magnesium dehydroabietate could improve mechanical properties and crystallization temperatures of PP and also decrease the size of spherulites. Kinetic analysis of PP isothermal crystallization showed that magnesium dehydroabietate decreased the fold surface energy of the developing crystals of PP and promoted the nucleation and crystallization of PP. However, calcium dehydroabietate increased the fold surface energy of the developing crystals of PP, but had no nucleation effect on PP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2644–2651, 2002     

Highly efficient nucleating additive for isotactic polypropylene studied by differential scanning calorimetry

The influence of an organic phosphate derivative in the crystallization of the monoclinic phase of isotactic polypropylene was studied by differential scanning calorimetry. To analyze the nucleation activity of the additive, the self‐nucleation process of the pure polymer was also studied by thermal techniques. A large increase in crystallization temperatures was obtained even for the lowest concentration of the additive, and its nucleating efficiency is the highest observed for α‐nucleating agents in isotactic polypropylene. The nucleating agent was also observed to increase the stability of the crystals formed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1669–1679, 2002; DOI 10.1002/app.10546     

Influence of chalk and its surface treatment on crystallization of filled polypropylene

Isotactic polypropylene has been shown to crystallize from the melt spherulitically at intermediate undercoolings (100–130°C) in the presence of a high amount (40 wt %) of chalk (calcium carbonate). Linear growth rate is not remarkably affected by the presence of a filler. Both nonisothermal and isothermal crystallization DSC experiments indicate that chalk acts as a weak nucleant. Introduction of liquid [oligomer of ethylene oxide (OEO), M_w = 300] at polymer–filler interface lowers the nucleating activity of chalk. Analysis of crystallization kinetics in Avrami coordinates, followed by dimensional-analysis correction for the case of nonintegral values of exponents, indicates that the amount of extra “chalk nuclei” is approximately constant in the range of 100–130°C while the amount of OEO-modified “chalk nuclei” decreases with the increase of the crystallization temperature. Comparison of the melting endotherms indicates that filled melt-crystallized material contains higher fraction of lower melting crystallites than unfilled polypropylene. This fraction is also higher in the case of polypropylene filled with unmodified chalk. Nucleating activity of chalk has been shown to depend upon its crystal structure (calcite or aragonite), surface topography, and aggregation.     

Influences of the chemical defects on the crystal thickness and their melting of isothermally crystallized isotactic polypropylene

Ziegler-Natta and Metallocene Catalysis isotactic polypropylene with different chemical defects were isothermally crystallized at various crystallization temperatures. The crystal thickness and their corresponding melting behavior were studied using small angle X-ray scattering, atomic force microscopy, optical microscopy, and differential scanning calorimetry. The equilibrium melt temperature of the samples was calculated from the Hofmann-Weeks extrapolation for the supercooling. Two lamellar populations were distinctly observed in all cases during the crystallization process. Relatively thicker and stable lamellar crystals which melt at higher temperatures were observed with lowering the supercooling and found catalysis dependence in these crystals. During melting, no significant recrystallization of the samples has been detected for higher crystallization temperature where recrystallization processes enhance the lamellae thickness. The melting of the crystals has found strong dependence with the crystallization temperatures, the catalysis process and the nature of the defects present in the isotactic polypropylene. The increase of the crystal lamellae thickness and their melting temperature might be presumably related with the chain folding mechanism as well as the stability of the crystals formed during the isothermal crystallization process. A combined plot of SAXS and DSC results is demonstrated for the equilibrium melting temperature followed by critical analysis of the results.     

Relating the molecular structure and crystallization behavior of polypropylene

The crystallization behavior of two polypropylene (PP) resins as used for biaxially oriented polypropylene (BOPP) and general injection mold applications, respectively, has been intensively investigated and compared by means of polarized light optical micrography (POM), differential scanning calorimetry (DSC), conventional transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM). It is found that both molecular weight distribution and isotacticity of polypropylene strongly affect its crystallization characteristics, e.g., the number of crystal nuclei at the initial stage, crystallization dynamics, the morphology, size and perfection of crystals in the final product, and so on. The results indicate an appropriate molecular structure is vital in producing high‐quality BOPP film. Polym. Eng. Sci. 44:1749–1754, 2004. © 2004 Society of Plastics Engineers.     

Biomineralization of calcium carbonate by adding aspartic acid and lysozyme

Calcium carbonate is one of the most abundant materials present in nature. Crystal structures of CaCO₃ become three polymorphic modifications, namely calcite, aragonite and vaterite. Polymorphic modifications are mediated by adding aspartic acid (Asp) and lysozyme. Lysozyme, which is a major component of egg white proteins, has influenced the calcification of avian eggshells. The influence of Asp and lysozyme on the crystallization of CaCO₃ was investigated by adding these additives and calcium chloride solution into sodium carbonate solution in a crystallization vessel. CaCO₃ crystals were analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Fourier transform infrared spectrometry (FT-IR). XRD was used to select the intensities and crystal structure of specific calcium carbonate. SEM was employed for the analysis of the morphology of the precipitation and particle size. Two kinds of crystals were identified by FT-IR spectrum. Hexagonal crystals of vaterite were affected by the Asp in the crystallization solution. However, rhombohedral crystals of calcite by lysozyme were formed without any sign of vaterite.     

Study of crystallization and melting behavior of polypropylene‐block‐polyethylenes copolymers fractionated from polypropylene and polyethylene mixtures

A series of ethylene–propylene block copolymer fractions of differing compositions, while still retaining broad molecular weight distributions, were obtained by fractionation of polypropylene (PP) and polyethylene (PE) copolymers prepared by sequential polymerization of ethylene and propylene. The crystallization and melting behavior of the polypropylene‐block‐polyethylene fractions were studied. It was observed that the major component could suppress crystallization of the minor component, leading to a decrease in crystallinity and melting temperature. Non‐isothermal crystallization showed that crystallization of the ethylene block was less influenced by composition and cooling rate than the propylene block. At fast cooling rates, the ethylene block could crystallize prior to the propylene block. Isothermal crystallization kinetics experiments were also conducted. We found that the block copolymers with minor ethylene components had smaller Avrami exponents (n ≈ 1.0), hence indicating a reduced growth dimension of the PE crystals by the pre‐existing PP crystals. On the other hand, the ethylene block exhibited much larger Avrami exponents in those block copolymers with major ethylene contents. Copyright © 2004 Society of Chemical Industry     

Effects of vibration blending on the subsequent crystallization behavior of polycarbonate/polypropylene blends

The effects of blending in a novel vibration internal mixer on the subsequent multiple crystallization of 70/30 w/w polycarbonate (PC)/polypropylene (PP) were investigated by differential scanning calorimetry, wide‐angle X‐ray diffractogram, and microscopy. The vibration internal mixer was reformed from a conventional internal mixer through parallel superposition of an oscillatory shear on a steady shear. For this polypropylene‐minor phase blend, three possible crystallization peaks were observed. The crystallization behavior was sensitive to the sizes and the size distribution of the dispersed polypropylene droplets. Larger amplitude and/or higher‐frequency vibration produced more small droplets (<2 μm) and increased the number of medium droplets (2–8 μm) as a result of the spatially wider and temporally quicker variation of shear rate. The resulting subsequent low‐temperature crystallization peak became larger and shifted to lower temperature, and the intermediate‐temperature peak became obvious. On the contrary, the coalescence of small droplets, resulting from the heating treatment, weakened the low‐temperature peak but strengthened the intermediate‐temperature peak and rendered the high‐temperature peak to be wider. Mixing at the too high amplitude produced the unstable, partially cocontinuous phase morphology restricting the medium droplets and enlarging the surface area, such that the intermediate‐temperature crystallization peak did not appear. Multiple crystallization was related to phase morphology and the nucleation density as well as surface effects. Double‐fusion endotherms of the PP component were also observed, corresponding to the melting of different forms of polypropylene crystals. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 92–103, 2002     

The cocrystallization behavior of binary blends of isotactic polypropylene and propylene-ethylene random copolymers

Rapidly crystallized blends of metallocene isotactic polypropylene and propylene-ethylene random copolymers with an ethylene content varying from 0.76 to 7 mol% were found to cocrystallize to different degrees depending on the composition of the comonomer and content of copolymer in the blend. The degree of molecular mixing was studied using differential scanning calorimetry and solvent extraction techniques. A high extent of cocrystallization is obtained in the whole composition range of blends with a copolymer having up to ～ 2 mol% of ethylene. The degree of cocrystallization decreases gradually with increasing ethylene content or with increasing copolymer content in the blend. It is found that for ethylene contents as high as 5–7 mol% the copolymer rich blends show partial separate crystallization of the propylene ethylene copolymer. Thus, these crystals were selectively extracted at temperatures just above the dissolution temperature of the pure copolymer. In these blends, the fractional content of segments from the copolymer molecules incorporated in the cocrystal is low, yet it prevents extraction of these molecules at temperatures above the dissolution temperature of the copolymer. The degree of cocrystallization is explained by differences in crystallization kinetics of the pure components. The percentage of extracted material was found to be directly related to the dissolution temperature of the cocrystal which was also found to be a linear function of the inverse of the crystallite thickness. The high extent of cocrystallization observed for these polypropylene blends contrasts with comparable blends of polyethylenes. The blends of linear PE with a copolymer of 4 mol% branch units and higher, form separate crystals even after rapid crystallization.     

The synthesis of vaterite and physical properties of PP/CaCO3 composites

Vaterite was synthesized in the emulsion state at 50 ‡C. The mixing method was found to have a significant effect on the shape of vaterite. In order to investigate the effect of CaCO₃ morphology on mechanical property and thermal property of polypropylene, cubic forms of calcite and needle forms of aragonite were also prepared in the emulsion states. When vaterite was used as a filler in the PP/CaCO₃ composites, the crystallization temperature and crystallinity were higher than those with other forms. In addition, the size of spherullite of polypropylene was the finest when vaterite was used. Therefore, the vaterite is considered as a proper nucleating agent for polypropylene.     

Morphological features and melting behavior of nanocomposites based on isotactic polypropylene and multiwalled carbon nanotubes

Nanocomposites based on low molar mass isotactic polypropylene (iPP) and a low concentrations (1–2 wt %) of multiwalled carbon nanotubes (MWCNTs) were studied using thermal analysis, optical and electronic microscopy, and X‐ray diffraction/scattering techniques. It was first determined that MWCNT decrease induction time and act as nucleating agents of the iPP crystals during nonisothermal crystallization. One of the consequences of the nucleation effect was that the original spherulitic morphology of iPP was transformed into a fibrillar‐like. The corresponding long period of the original well‐defined lamellar structure slightly increased suggesting the formation of thicker crystals in samples containing MWCNT. The nature of the α‐iPP crystalline structure was not affected by MWCNT. After nonisothermal crystallization, two melting endotherms were present during thermal scanning of the iPP/MWCNT nanocomposites their proportion changing with the heating rate. After resolving the total DSC signal in its components using MDSC, the overall evolution of such behavior could be explained in terms of the melting/recrystallization mechanism. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thermal properties and isothermal crystallization of syndiotactic polypropylenes: Differential scanning calorimetry and overall crystallization kinetics

Isothermal crystallization and subsequent melting behavior of five samples of syndiotactic polypropylene are presented. Crystallization studies were carried out in the temperature range of 60°C to 97.5°C using a differential scanning calorimeter (DSC). Subsequent DSC scans of isothermally crystallized samples exhibited double melting endotherms. The high melting peak was concluded to be the result of the melting of crystals formed by recrystallization during the reheating process. Overall crystallization kinetics was studied based on the traditional Avrami analysis. Analysis of crystallization times based on the modified growth rate theory suggested that, within the crystallization temperature range studied, the syndiotactic polypropylenes crystallize in regime III. Kinetic crystallizability parameters also were evaluated, and were found to be in the range of 0.41°C s⁻¹ to 2.14°C s⁻¹. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 44–59, 2000     

超高分子质量聚丙烯冻胶纤维的结晶性能研究

采用冻胶纺丝法制备超高分子质量聚丙烯纤维（UHMWPP）,并在不同的拉伸温度下对其进行拉伸。研究了在相同的拉伸倍率下,拉伸温度对UHMWPP纤维结晶性能、热性能的影响。结果表明：UHMWPP纤维结晶晶体间存在很多间隙;纤维的结晶性能和耐热性能都随拉伸温度的提高而提高。     

退火工艺对PP–R复合材料性能的影响

通过注塑工艺制备无规共聚聚丙烯(PP–R)样条,并将样条置于热处理设备进行退火处理。运用差示扫描量热仪、广角X射线衍射仪、偏光显微镜和扫描电子显微镜等方法,分析了退火对PP–R的结晶行为和力学性能的影响。结果表明,退火可以消除热应力,促进结晶的完善,使得PP–R的结晶度从41.2%提高到48.4%,诱导β晶的生成,能有效改善材料的力学性能。退火使得PP–R的拉伸强度有所提高;对冲击性能影响明显,在25℃时,PP–R的冲击强度从41.67 k J/m2提高到66.84 k J/m2,提高了60.4%;在0℃时,PP–R的冲击强度从11.54 k J/m2提高到32.68 k J/m2,提高了1.8倍。     

Enhanced mechanical properties for porous ceramics with an in situ formation of anorthite crystals during vitrification

Porous anorthite ceramics are widely applied as catalysis supports, separation membranes, and thermal insulations at high temperatures. In situ formation of anorthite crystals during vitrification is herein employed to improve mechanical properties of porous anorthite with modulated grain sizes on pore walls. Sintering parameters of shrinkage (5%–30%), open porosity (31.0%–58.3%), density (1.18–1.71 g/cm³), and mass loss (12.20%–18.26%) are estimated to investigate the influences of sintering aids of calcite, fused mullite, and silicon carbide or talcum on the densification processes of porous anorthite. The Kissinger equation is used to determine the activation energy of 783 kJ/mol for the crystallization of anorthite, which is significantly low for the formation of anorthite crystals through surface nucleation mechanism in present flux-rich melt. In situ crystallization and simultaneous densification under liquid drainages are favored for whiskers-reinforced mechanism to enhance flexural strengths (6.9–19.4 MPa) for porous anorthite with the porosity of 49.6%–58.3% through the formation of hierarchical nano- and microscale structures during vitrification.     

Controlled Crystallization of Calcite Under Surface Electric Field Due to Polarized Hydroxyapatite Ceramics

We examined effects of surface electric fields for the crystallization of calcite on polarized hydroxyapatite ceramics with and without polyacrylic acid (PAA) as soluble additive. Both on negatively and positively charged surfaces without PAA, the only precipitates were rhombohedra calcite crystals with the face of the {10.4} plane favorably oriented parallel to the surfaces. This oriented growth was explained by the nucleation theory in the presence of an external electric field. However, the addition of PAA drastically changed the situation of the calcite crystals, i.e., the crystallites were the hemispheric aggregates of calcite needles with a facetted rhombohedral {10.4} end face and flat island-shaped aggregates of ones with a rough (00.1) end face having a triangular shape. The calcite needles grew along the crystallographic [00.1] axis. This oriented growth was explained by epitaxy on the PAA–Ca²⁺ complexes adsorbing on the surfaces. The morphology of the PAA–Ca²⁺ complex assemblies adsorbing on the surfaces before the calcite nucleation was an important factor to control the structure of calcite aggregates formed following. This morphology was controlled by properties of the surface electric field and the spatial distribution of the negatively and positively charged sites in the PAA–Ca²⁺ complexes.     

Calorimetric analysis of the multiple melting behavior of poly(L‐lactic acid)

This article contains a detailed calorimetric analysis of the multiple melting behavior of poly(L ‐lactic acid) (PLLA) in dependence of crystallization conditions. PLLA crystals formed upon primary crystallization have a greater tendency to reorganize into more stable structures during the heating scan that leads to fusion. Depending on crystallization temperature, one or multiple melting endotherms and/or reorganization exotherms can be evidenced. This complex melting behavior arises from the fusion of a certain amount of the original crystals (already partially perfected during the heating scan), followed by recrystallization and final melting of more perfect crystals, partly grown during primary crystallization, and partly formed through the reorganization processes occurring during the heating scan. A detailed map of the melting behavior of PLLA is described in this contribution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3145–3151, 2006