三种有机成核剂成核聚丙烯的非等温结晶动力学研究

采用DSC研究了聚丙烯（PP）和三种有机成核剂成核的PP在不同的降温速率下的非等温结晶动力学。用Avrami对DSC的测试结果进行了分析。结果表明,三种有机透明成核剂能显著提高PP的结晶温度和结晶速率。可以用修正Avrami方程的Jeziorny法来处理三种有机成核剂成核PP的非结晶等温结晶行为,处理结果表明：三种有机成核透明成核剂成核PP的半结晶时间减少,结晶动力学常数(Zc)增加,结晶速率增加;松香型成核剂能最快提高PP的结晶速率;同一降温速率下,三种有机成核透明剂成核PP的n值较纯PP减少,结晶成核方式发生了改变。     

Detecting crystallization structure evolution of polypropylene injection‐molded bar induced by nucleating agent

The crystallization structures of Polypropylene (PP) injection‐molded bars nucleated by nucleating agent were detected from the skin layer to the core zone, layer by layer. α‐phase nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase nucleating agent aryl amides compounds (TMB‐5), and their compounds were introduced into PP matrix, respectively. The relative content of β‐phase PP in the different zones of an injection‐molded bar was characterized and calculated by Wide angle X‐ray diffraction (WAXD) and Differential scanning calorimetry (DSC). The results show that, whether in pure PP or in nucleated PP, both β‐phase PP and α‐phase PP grow in the skin layer of the injection‐molded bar. However, in the intermediate layers and the core zone, the crystallization structures of PP are dependent on the used nucleating agent. β‐phase is the main crystallization structure of TMB‐5 (0.1 and 0.2 wt%) nucleated PP, and α‐phase in DMDBS (0.1 and 0.2 wt%) nucleated PP. Compounding nucleating agents with 0.1 wt% DMDBS and 0.1 wt% TMB‐5 induces PP crystallization almost in β‐phase; however, PP nucleated by 0.2 wt% DMDBS and 0.2 wt% TMB‐5 crystallizes exclusively in α‐phase. The crystallization mechanism of PP nucleated by compounding nucleating agents was further studied in this work. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Non‐isothermal crystallization kinetics of cork‐polymer composites for injection molding

The non‐isothermal crystallization behavior of cork–polymer composites (CPC) based on polypropylene (PP) matrix was studied. Using differential scanning calorimetry (DSC), the crystallization behavior of CPC with 15 wt % cork powder at different cooling rates (5, 10, 15, and 20 °C/min) was studied. The effect of a coupling agent based on maleic anhydride was also analyzed. A composite (PPg) containing polypropylene grafted maleic anhydride (PPgMA) and PP was prepared for comparison purposes. Crystallization kinetic behavior was studied by Avrami, Ozawa, Liu, and Kissinger methods. The Ozawa method fails to describe the behavior of these composites. Results show that cork powder surface acts as a nucleating agent during non‐isothermal crystallization, while the addition of PPgMA decreases the crystallization rate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44124.     

Crystallization behavior and crystallite morphology control of poly(L‐lactic acid) through N,N′‐bis(benzoyl)sebacic acid dihydrazide

Adding a nucleating agent is one of the best ways to accelerate the crystallization rate of poly(L ‐lactic acid) (PLLA) so as to obtain a high degree of crystallinity during the process, which will improve the heat distortion temperature of final products. In the work reported, N, N′‐bis(benzoyl)sebacic acid dihydrazide (BSAD) was synthesized and used as a nucleating agent for PLLA. Isothermal and non‐isothermal crystallization behaviors were investigated using differential scanning calorimetry (DSC). The addition of BSAD successfully enhances the crystallization rate of PLLA. A unique phase separation behavior of PLLA/BSAD blends is found from DSC as well as from polarized optical microscopy, which explains the difference of optimal BSAD concentration between isothermal and non‐isothermal crystallization. This is the first recording of a phase separation peak in PLLA/nucleating agent blends using DSC. In thermogravimetric analysis, the enhanced thermal stability indicates that there are strong hydrogen bonds between BSAD and PLLA matrix. BSAD can dissolve in PLLA melt below its melting point through intermolecular hydrogen bonding with PLLA and self‐assemble upon cooling, leading to the surface being capable of nucleating PLLA. Different phase separation temperatures can be used to control the morphology of BSAD, which finally determines the crystallite morphology of PLLA. © 2012 Society of Chemical Industry     

A highly active and selective β‐nucleating agent for isotactic polypropylene and crystallization behavior of β‐nucleated isotactic polypropylene under rapid cooling

Zinc adipate (Adi‐Zn) was observed to be a highly active and selective β‐nucleating agent for isotactic polypropylene (iPP). The effects of Adi‐Zn on the mechanical properties and the β‐crystals content of nucleated iPP were investigated. The impact strength of iPP nucleated with 0.2 wt % Adi‐Zn was 1.8 times higher than that of neat iPP. In addition, wide‐angle X‐ray diffraction analysis indicated that the content of β‐crystals in nucleated iPP (k_β value) reached 0.973 with 0.1 wt % Adi‐Zn, indicating that Adi‐Zn is a highly active and selective β‐nucleating agent for iPP. Furthermore, fast scanning chip calorimetry (FSC) studies using cooling rates from 60 to 13,800 °C min^?1 revealed that the formation of β‐crystals significantly depended on the cooling rates. At cooling rates below 3000 °C min^?1, only β‐crystals existed. However, at cooling rates above 6000 °C min^?1, β‐crystals failed to form. Moreover, a lower critical crystallization temperature that corresponded to the generation of β‐crystals was investigated using cooling‐induced crystallization, and the results are in good agreement with those of a previous study. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43767.     

Variation of non‐isothermal crystallization behavior of isotactic polypropylene with varying β‐nucleating agent content

The non‐isothermal crystallization behavior, the crystallization kinetics, the crystallization activation energy and the morphology of isotactic polypropylene (iPP) with varying content of β‐nucleating agent were investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The DSC results showed that the Avrami equation modified by Jeziorny and a method developed by Mo and co‐workers could be successfully used to describe the non‐isothermal crystallization process of the nucleated iPPs. The values of n showed that the non‐isothermal crystallization of α‐ and β‐nucleated iPPs corresponded to a tridimensional growth with homogeneous and heterogeneous nucleation, respectively. The values of crystallization rate constant showed that the rate of crystallization decreased for iPPs with the addition of β‐nucleating agent. The crystallization activation energy increased with a small amount (less than 0.1 wt%) of β‐nucleating agent and decreased with higher concentration (more than 0.1 wt%). The changes of crystallization rate, crystallization time and crystallization activation energy of iPPs with varying contents of β‐nucleating agent were mainly determined by the ratio of the content of α‐ and β‐phase in iPP (α‐PP and β‐PP) from the DSC investigation, and the large size and many intercrossing lamellae between boundaries of β‐spherulites for iPPs with small amounts of β‐nucleating agent and the small size and few intercrossing bands among the boundaries of β‐spherulites for iPPs with large amounts of β‐nucleating agent from the SEM examination. Copyright © 2010 Society of Chemical Industry     

Crystalline morphology and dynamical crystallization of antibacterial β‐polypropylene composite

The crystalline morphology and dynamical crystallization of antibacterial polypropylene composite and pure polypropylene were investigated via differential scanning calorimeter (DSC), wide angle X‐ray diffraction (WAXD), and real‐time hot‐stage optical microscopy (OM). The results reveal that the crystalline morphology of antibacterial PP composites changes with variations of the crystallization conditions and compositions. The crystalline phase consists of both α‐PP and β‐PP crystals. The content of β‐PP decreases with the increase in antibacterial agent content and cooling rate. With the addition of β‐nucleating agent, the morphologies of all dynamically crystallized antibacterial PP composites show no obvious spherulitic morphology, and the decrease of crystal perfection and the increase of nucleation density of antibacterial PP composite system could be observed. With the increase of antibacterial agent content, the overall crystallization rates of the antibacterial PP composite increase dramatically, while the content of β‐PP in all antibacterial PP composite decrease distinctly under given cooling conditions. These results can be explained by the interruptive effect of antibacterial agent on interactions of β‐nucleating agent components and the obstructing effect of antibacterial agent on the mobility of PP chains in melts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and nonisothermal crystallization behavior of polypropylene/layered double hydroxide nanocomposites

Polypropylene (PP)/layered double hydroxide (LDH) nanocomposites were prepared via melt intercalation using dodecyl sulfate anion modified LDH and maleated PP as compatibilizing agent. Evidently the interlayer anions in LDH galleries react with maleic anhydride groups of PP-g-MA and lead to a finer dispersion of individual LDH layers in the PP matrix. The nanostructure was characterized by XRD and TEM; the examinations confirmed the nanocomposite formation with exfoliated/intercalated layered double hydroxides well distributed in the PP matrix. The nonisothermal crystallization behavior of resulting nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. In nonisothermal crystallization kinetics, the Ozawa approach failed to describe the crystallization behavior of nanocomposites, whereas the Avrami analysis and Jeziorny method well define the crystallization behavior of PP/LDH nanocomposite. Combined Avrami and Ozawa analysis (Liu model) also found useful. The results revealed that very small amounts of LDH (1%) could accelerate the crystallization process relative to the pure PP and increase in the crystallization rates was attributed to the nucleating effect of the nanoparticles. Polarized optical microscopy (POM) observations also support the DSC results. The effective crystallization activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. Overall, results indicated that the LDH particles in nanometer size might act as nucleating agent and distinctly change the type of nucleation, growth and geometry of PP crystals.     

Nucleation‐controlled dual semicrystalline morphology of polyamide 11

Crystallization of polyamide 11 at low supercooling of the melt proceeds via heterogeneous nucleation and spherulitic growth of lamellae, while at temperatures close to the glass transition homogeneous nucleation prevails, preventing spherulite formation and leading to formation of a large number of nanometer‐sized mesophase domains. It is shown that spherulitic and non‐spherulitic crystallization at low and high supercooling of the melt, respectively, can be enforced by tailoring the cooling conditions, causing a twofold semicrystalline morphology at ambient temperature. Analysis of non‐isothermal crystallization as a function of the cooling rate, using fast scanning chip calorimetry, reveals that in the case of polyamide 11 such twofold semicrystalline morphology is predicted when cooling at rates between about 20 and 200 K s^?1, since then two separate crystallization events are observed. The prediction has been confirmed by preparation of films crystallized during ballistic cooling at different rates which then were analyzed regarding their structure using optical microscopy, X‐ray diffraction and calorimetry. The study is completed by discussion of implications of twofold non‐isothermal crystallization for structure evolution in polymer processing, as well as by providing information that such behavior is not only typical for polyamide 11 but also for isotactic polypropylene or poly(butylene terephthalate) as two further examples. © 2018 Society of Chemical Industry     

Crystallization behavior of carbon black‐filled polypropylene and polypropylene/epoxy composites

The crystallization behavior of polypropylene (PP)/carbon black (CB) and PP/epoxy/CB composites was studied with differential scanning calorimetry (DSC). The effects of compatibilizer MAH‐g‐PP and dynamic cure on the crystallization behavior are investigated. The nonisothermal crystallization parameters analysis showed that CB particles in the PP/CB composites and the dispersed epoxy particles in the PP/epoxy composites could act as nucleating agents, accelerating the crystallization of the composites. Morphological studies indicated that the incorporation of CB into PP/epoxy resulted in its preferential localization in the epoxy resin phase, changing the spherical epoxy particles into elongated structure, and thus reduced the nucleation effect of epoxy particles. Addition of MAH‐g‐PP significantly decreased the average diameter of epoxy particles in the PP/epoxy and PP/epoxy/CB composites, promoting the crystallization of PP more effectively. The isothermal crystallization kinetics and thermodynamics of the PP/CB and PP/epoxy/CB composites were studied with the Avrami equation and Hoffman theory, respectively. The Avrami exponent and the crystallization rate of the PP/CB composites were higher than those of PP, and the free energy of chain folding for PP crystallization decreased with increasing CB content. Addition of MAH‐g‐PP into the PP/epoxy and PP/epoxy/CB composites increased the crystallization rate of the composites and decreased the chain folding energy significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 104–118, 2006     

Effect of syndiotactic polystyrene on the crystallization behavior of isotactic polypropylene/syndiotactic polystyrene blends with and without β‐nucleating agent

Blends of isotactic polypropylene (PP) and syndiotactic polystyrene (sPS) with and without β‐nucleating agent were prepared using a twin‐screw extruder at 290 °C. Blends of PP/sPS with β‐nucleating agent mainly show β crystalline form, irrespective of high (20 °C min^?1) or low (2 °C min^?1) previous cooling rates. This suggests that the cooling rates have little effect on the polymorphic composition of PP in PP/sPS blends. The effect of sPS on the crystallization of PP is compared with that of polyamide 6 (PA6). The increase in crystallization temperature of PP is smaller in the presence of sPS than in the presence of PA6; the fold surface free energy of PP/sPS is larger than that of PP/PA6 blends. These results reveal that compared with PA6, sPS has much weaker α‐nucleation effect on the crystallization of PP. The weak α‐nucleation effect of sPS is attributed to the high lattice mismatch between PP and sPS crystals.     

Effect of continuous oscillatory shear on isothermal crystallization of non‐nucleated and nucleating‐agent‐treated isotactic polypropylene assessed by dynamic mechanical analysis

Using dynamic mechanical analysis (DMA), we investigated the in situ crystallization kinetics of non‐nucleated and nucleating‐agent‐treated isotactic polypropylene (iPP) under continuous oscillatory shear during the entire crystallization process, and then compared the DMA results with those measured using differential scanning calorimetry under conventional quiescent crystallization. Our analyses, based on the Avrami equation, show that continuous oscillatory shear accelerated crystallization of non‐nucleated iPP, but interfered with crystallization for nucleating‐agent‐treated iPP. Our results indicate that, for the present nucleating agent, its accelerating effect on crystallization cannot coexist with the accelerating effect of shear on crystallization. We attributed this difference to the disruptive effect of shear on growth and the different nucleation models of non‐nucleated and nucleating‐agent‐treated iPP. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41685.     

Comparative study of the nucleation activity of third‐generation sorbitol‐based nucleating agents for isotactic polypropylene

The nucleation activity of the sorbitol derivatives 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) and methyldibenzylidene sorbitol are compared with that of talc, a conventional nucleating agent for the monoclinic crystalline phase of isotactic polypropylene. The thermal parameters associated with the dynamic crystallization process are studied as a function of the cooling rate by differential scanning calorimetry, and the nucleating efficiency is assessed by comparison with self‐nucleation, the highest values being observed for 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) over the whole concentration range. The nature of the polymer crystals formed in the nucleated polymer was studied by X‐ray diffraction, and the data show an increase in a preferred orientation of the polymer crystallites with increasing concentration of nucleating agent. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2440–2450, 2002     

Influence of a novel β‐nucleating agent on the structure,morphology, and nonisothermal crystallization behavior of isotactic polypropylene

The crystalline structure, morphology, and nonisothermal crystallization behavior of isotactic polypropylene (iPP) with and without a novel rare earth‐containing β‐nucleating agent (WBG) were investigated with wide‐angle X‐ray diffraction, polar optical microscopy, and differential scanning calorimetry. WBG could induce the formation of the β form, and a higher proportion of the β form could be obtained by the combined effect of the optimum WBG concentration and a lower cooling rate. The content of the β form could reach more than 0.90 in a 0.08 wt % WBG nucleated sample at cooling rates lower than 5°C/min. Polar optical microscopy showed that WBG led to substantial changes in both the morphological development and crystallization process of iPP. At all the studied cooling rates, the temperature at which the maximum rate of crystallization occurred was increased by 8–11°C in the presence of the nucleating agent. An analysis of the nonisothermal crystallization kinetics also revealed that the introduction of WBG significantly shortened both the apparent incubation period for crystallization and the overall crystallization time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of the amount of salts of rosin acid on the nonisothermal crystallization,morphology, and properties of isotactic polypropylene

The nonisothermal crystallization of Isotactic polypropylene (iPP) containing different concentration of nucleating agent potassium dehydroabietate (DHAA‐K) or sodium dehydroabietate (DHAA‐Na) at the cooling rate of 10°C/min was investigated using differential scanning calorimetry (DSC) together with Jeziorny's method. It was found that the temperature at which the maximum rate of crystallization occurred shifted to a higher region by about 13.7–16.9°C, and the rate of crystallization became faster for iPP with DHAA‐K (PPK) or DHAA‐Na (PPNa) in comparison to the virgin iPP. Avrami exponent for virgin PP, PPK, and PPNa was about 3.1, 2.2, and 2.2, respectively, suggesting the change of the crystal growth mechanism of iPP with the addition of the nucleating agents. The morphology of iPP with and without nucleating agent examined by a cross polarized light microscope indicated that the size of spherulites marginally decreased, which then remained stable with the increase of the concentration of DHAA‐K or DHAA‐Na. The measurements of the optical and mechanical properties of iPP showed that the transparency, gloss, and flexural modulus increased with increasing nucleating agent before its optimal concentration. POLYM. ENG. SCI., 47:889–897, 2007. © 2007 Society of Plastics Engineers     

Fast crystallization of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) with talc and boron nitride as nucleating agents

The crystallization behavior of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) induced by two kinds of nucleating agents, boron nitride (BN) and talc, was investigated by differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both BN and talc have good nucleating ability in the crystallization of PHB and PHBV. From these results, combined with molecular weight measurement by gel permeation chromatography, the mechanism of nucleation by BN and talc in the crystallization of PHB and PHBV has been proposed. BN acts as a nucleating agent itself and initiates nucleation in the crystallization of PHB and PHBV. Talc acts in a different way. It reacts as a chemical reagent with the molten chains of PHB/PHBV, while the reaction product acts as the true nucleating agent, which lowers the crystallization barriers of PHB and PHBV. ¹H NMR spectroscopy provides evidence for the reaction between PHB and talc and supports the proposed nucleation mechanism. Copyright © 2005 Society of Chemical Industry     

Polypropylene/linear low‐density polyethylene blends: Morphology,crystal structure,optical, and mechanical properties

The morphology, crystal structure, crystallization behavior, optical, and mechanical properties of isotactic polypropylene (iPP) blended with metallocene linear low‐density polyethylene (mLLDPE) and Ziegler–Natta linear low‐density polyethylene (zLLDPE), with and without nucleating agents, were investigated. The correlation between the structures and optical properties was investigated. The addition of linear low‐density polyethylenes (LLDPEs), nucleating agents, and poly(ethylene‐co‐octene) (POE) had little influence on the crystal form of the iPP. The growth along the b axis was favorable in the presence of nucleating agents and LLDPEs. The LLDPEs led to much finer crystal morphologies, and the nucleating agents further prohibited spherulite formation; consequently, light scattering from the bulk crystalline structure was reduced. In all blends, biphase morphology was observed, and POE could improve the adhesion between the iPP and mLLDPE. After blending with LLDPEs, the haze and stiffness decreased, and the gloss increased. mLLDPE enhanced the toughness whereas zLLDPE had a slight influence on it. The nucleating agents decreased the haze, increased the gloss more, and ameliorated the stiffness; however, they changed the toughness little. POE increased the toughness of the blend significantly, accompanied by a much lower haze, higher gloss, and almost the same stiffness. When the concentration of 1,3 : 2,4‐bis(3,4‐dimethyl‐benzylidene sorbitol) exceeded 0.25 wt %, the optical properties and mechanical properties leveled off. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of cross‐linked LLDPE/PP blend (LLDPE‐PP) as compatibilizer on morphology,crystallization behavior and mechanical property of LLDPE/PP blends

Moderate cross‐linked blend (LLDPE‐PP) of linear low‐density polyethylene (LLDPE) and polypropylene (PP) with benzoyl peroxide (BPO) were prepared by the reactive melt mixing in HAAKE mixer. Effect of LLDPE‐PP as compatibilizer on the morphology, crystallization behavior and mechanical properties of LLDPE/PP (87/13) blends were studied using scanning electron microscopy (SEM), polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and mechanical testing machines. The results showed that LLDPE‐PP not only improved the interfacial adhesion between the LLDPE and PP but also acted as selective nucleating agent for crystal modification of PP. In the blends, the sizes of LLDPE and PP spherulites became smaller, and their melting enthalpies reduced in the presence of LLDPE‐PP. Furthermore, the mechanical properties of LLDPE/PP blends were improved with the addition of LLDPE‐PP, and when the concentration of LLDPE‐PP was 2 phr, the ternary blend had the best mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization characteristics of isotactic polypropylene with and without nucleating agents

Nucleation effects of two sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). A nonisothermal crystallization kinetic equation was employed to analyze the crystallization characteristics of iPP with or without the nucleating agents from DSC crystallization thermograms. The equilibrium melting temperature of iPP necessary for the kinetic study was obtained by the extrapolation method to be 209°C. The nonisothermal crystallization kinetic analysis for the unnucleated iPP at different cooling rates was possible by assuming the spherulite growth initiated simultaneously by heterogeneous and homogeneous nucleation. On the other hand, the crystallization kinetics of the nucleated iPP could be described by the heterogeneous nucleation and growth process alone. The addition of the nucleating agents up to their saturation concentrations in iPP increased the crystallization peak temperature by 17°C, and the number of effective nuclei by three orders of magnitude. A high concentration of the nucleating agents caused agglomeration of the agents to lower the number of effective nuclei.     

Thermal and crystallization behavior of silane‐crosslinked polypropylene

Silane‐crosslinked polypropylene (PP) has been prepared first by the grafting of silane onto the backbone of PP in a melt process and then by crosslinking in warm water. The effects of type and concentration of silane and peroxide on the silane grafting on PP were investigated. The thermal behavior of the silane‐crosslinked PP was studied by thermogravimetric (TG) and differential scanning calorimetry (DSC) methods. TG results show that PP prepared via silane crosslinking increases its thermal stability greatly. It has been found from DSC measurements that the crystallization temperatures, ie the onset temperature and peak temperature of the exotherm of the silane‐crosslinked PP, increase compared with those of the pure PP. The silane crosslinking hardly changes the crystallinity degree of PP. The crystallization behavior of the silane‐crosslinked PP was also studied by wide‐angle X‐ray diffraction analysis. Copyright © 2004 Society of Chemical Industry