DSC and TMDSC study of melting behaviour of poly(butylene succinate) and poly(ethylene succinate)

The subsequent melting behaviour of poly(butylene succinate) (PBSU) and poly(ethylene succinate) (PES) was investigated using DSC and temperature modulated DSC (TMDSC) after they finished nonisothermal crystallization from the melt. PBSU exhibited two melting endotherms in the DSC traces upon heating to the melt, which was ascribed to the melting and recrystallization mechanism. However, one melting endotherm with one shoulder and one crystallization exotherm just prior to the melting endotherm were found for PES. The crystallization exotherm was ascribed to the recrystallization of the melt of the crystallites with low thermal stability, and the shoulder was considered to be the melting endotherm of the crystallites with high thermal stability. The final melting endotherm was ascribed to the melting of the crystallites formed through the reorganization of the crystallites with high thermal stability during the DSC heating process. TMDSC experiments gave the direct evidences to support the proposed models to explain the melting behaviour of PBSU and PES crystallized nonisothermally from the melt.     

Largely improved crystallization behavior and thermal stability of poly(L‐lactide) via the synergistic effects of graphene oxide and carbon nanotubes

Graphene oxide (GO) and carbon nanotubes (CNTs) and their compound were introduced into semicrystalline poly(l ‐lactide) (PLLA) to prepare the corresponding binary and/or ternary nanocomposites, respectively. The dispersion states of nanofillers in different nanocomposites were investigated using UV‐Vis spectroscopy, scanning electron microscopy (SEM) and rheological measurement. The results showed that when GO and CNTs were simultaneously present in the PLLA matrix, good dispersion states of both GO and CNTs could be achieved and the ternary nanocomposites exhibited percolated network structure. The effects of different nanofillers on the crystallization behavior of PLLA matrix were comparatively investigated under the different crystallization conditions including melt crystallization process (nonisothermal and isothermal crystallization from the melt) and cold crystallization (crystallization occurring from an amorphous state during the annealing process). The results showed that GO and CNTs exhibited apparent synergistic effects in improving crystallization ability and enhancing crystallinity of PLLA matrix. Study on the thermal stability of nanocomposites showed that the presence of nanofillers greatly improved the thermal stability of PLLA matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40143.     

Kinetics of isothermal and non‐isothermal crystallization of poly(butylene terephthalate)/ liquid crystalline polymer blends

The melting behavior and isothermal and non‐isothermal crystallization kinetics of poly(butylene terephthalate) (PBT)/thermotropic liquid crystalline polymer (LCP), Vectra A950 (VA) blends were studied by using differential scanning calorimetry. Isothermal crystallization experiments were performed at crystallization temperatures (T_c), of 190, 195, 200 and 205°C from the melt (300°C) and analyzed based on the Avrami equation. The values of the Avrami exponent indicate that the PBT crystallization process in PBT/VA blends is governed by three‐dimensional morphology growth preceded by heterogeneous nucleation. The overall crystallization rate of PBT in the melt blends is enhanced by the presence of VA. However, the degree of PBT crystallinily remains almost the same. The analysis of the melting behavior of these blends indicates that the stability and the reorganization process of PBT crystals in blends are dependent on the blend compositions and the thermal history. The fold surface interfacial energy of PBT in blends is more modified than in pure PBT. Analysis of the crystallization data shows that crystallization occurs in Regime II across the temperature range 190°C‐205°C. A kinetic treatment based on the combination of Avrami and Ozawa equations, known as Liu's approach, describes the non‐isothermal crystallization. It is observed that at a given cooling rate the VA blending increases the overall crystallization rate of PBT.     

Predictive Modeling of Non-Isothermal Crystallization in the Solidification of Polyoxymethylene Melt

The predictive modeling of non-isothermal crystallization of polyoxymethylene (POM) melt was proposed based on an isothermal crystallization experiment. The development of crystallinity and crystallization morphological evolution was simulated by considering the process of crystallization includes the three steps: nucleus, growth and ripening and the pre-ripened degree was considered explicit simultaneously. Double-scale computational modeling of the solidification phase transition of the semi-crystalline polymer POM melt was then numerical implemented. The heat flow equation coupling the evolution of crystallinity was computed by the finite different numerical method. The result of the cooling stage of POM melt shows the method can produce more visual information about the processing of crystallize and a relative reasonable detail about the temperature field.     

熔融结晶的过程强化

熔融结晶作为一种绿色高效的分离技术具有选择性高、能量消耗低、无须溶剂参与等优势,但在结晶理论研究、连续化生产、专用结晶器设计和工业放大等方面仍面临挑战。熔融结晶分离效率受物系性质、原料纯度和晶体生长速率限制。因此,熔融结晶过程的合理设计和过程优化对提高熔融结晶技术的能量和过程效率具有重要意义。基于熔融结晶技术在化工分离过程中的实际需求和应用前景,从熔融结晶过程工艺优化、晶体层生长表面设计、过程工艺耦合三方面论述熔融结晶过程中晶体成核、生长的强化方式,为达到高效率、低能耗的熔融结晶分离过程提供可行性指导。最后,概述了目前熔融结晶技术的主要研究焦点并对发展方向进行了展望。     

丙交酯的提纯技术

对丙交酯提纯技术,包括萃取,精馏,熔融,结晶技术作了介绍,分析了不同工艺的优缺点,并从工程设计的角度进行总结,指出熔融结晶技术能耗低,操作灵活,绿色环保,是一个相对比较适合的分离提纯技术。     

降膜结晶分离技术实验研究

采用萘－硫茚物系对新型高效降膜结晶技术的分离提纯机制进行了实验研究．考察了管外降膜结晶过程中结晶时间、料液流量、冷却水初始进口温度、冷却水降温速率及原料浓度对分离提纯效果的影响．实验发现降膜结晶过程中晶层生长并不完全是光滑界面的生长,而在某些条件下表现为粗糙界面的生长,即生长过程在某些条件下表现为两相区界面的生长．进一步对辅助提纯－发汗过程的工艺参数—发汗时间、发汗初始浓度的影响进行了实验研究．实验结果可用于降膜结晶传热传质机理的数值模拟．     

In situ atomic force microscopy of the melting of melt-crystallized polyethylene

High temperature AFM is used to observe the melting of polyethylene lamellae crystallized from the melt in situ in real-time. Both oriented and un-oriented samples are observed. The melting of shish-kebab structures, including revealing the bare oriented shish, is achieved. Lamellae are observed to melt from their edges, and this is proposed to be due to the inherent higher mobility at the crystal edges rather than differences in stability within the crystal due to different levels of post crystallization perfecting. Observation of the melting of structures that have been observed during growth confirms that material crystallized at lower temperatures melts first, followed by material crystallized in confined geometries, and finally the rest of the isothermally crystallized lamellae that melt back from the edges with an apparently random morphology that is not the reverse of the growth process. In situ observation during melting is confirmed as an alternative and complementary technique to etching to reveal behaviour during crystallization when crystallization is too rapid for in situ observation.     

Melt Entrapment and the Effective Distribution Coefficient during the Growth of a Crystal Layer

Methods for calculating the separation efficiency during the growth of a crystal layer from a binary melt are considered. It is shown that the amount of the mother liquor entrapped by a broken crystallization front and the effective distribution coefficient are determined by the ratio of actual and equilibrium temperature gradients near the surface of the growing layer. Theoretical results are in fair agreement with experimental data.     

分子量分布对聚酯性能的影响

研究了不同分子量分布聚酯的热性能、结晶性能和熔体挤出性能。结果表明,随分子量分布加宽,熔体结晶峰的峰温逐步升高,过冷程度降低,蜂形由宽矮形变为高尖形,而冷结晶峰峰温逐渐降低,峰形由宽变窄。同时,随分布加宽,结晶速度加快。在等混结晶过程中,在180℃附近出现结晶速度极大值,而且此极大值与分子量分布无关。此外,随分子量分布加宽,聚酯热稳定性略为下降,在熔体挤出过程中的粘度降增大,挤出过程迅速恶化,以致于难以成形。     

Morphological,rheological and thermal studies in melt processed compatibilized PA6/ABS/clay nanocomposites

Multicomponent compatibilized blends of polyamide 6 (PA6) and styrene-butadiene-acrylonitrile (ABS) with co-continuous morphology are among commercial alloys with an interesting combination of properties. To further enhance the properties different amounts of nanoclay were incorporated into these blends through a one step melt mixing process. The effect of nanoclay addition on rheological, thermal stability, crystallization and morphological properties of the nanocomposites were investigated and compared with those of the neat blends. The nanoscale dispersion of the clay layers in the blends were confirmed through X-ray diffraction and transmission electron microscopy methods. Rheological investigation indicated an increased viscosity and melt elasticity for the nanocomposite systems. The viscosity of nanocomposites followed a shear thinning flow behavior and decreased with increasing shear rates. The changes in the rheological properties were accompanied by refinement of the co-continuous morphology. For thermal degradation under N₂ atmosphere, the onset and maximum of degradation temperatures for the nanocomposites were as high as the neat blends, while significant improvement in thermal stability (about 60 °C by 3 wt% clay addition) was observed in the air environment. In addition agglomerated clay particles did not significantly affect thermal stability of the polymer matrix. Non-isothermal crystallization results indicated that the clay layers had a retarding effect on the crystal growth rate and facilitated the formation of α crystalline form. In addition no nucleation effect was observed during the crystallization process due to incorporation of nanoclay into the blends.     

四苯基氯化鏻对聚偏氟乙烯电活性相的诱导作用

通过简单的熔体共混方法,将不同质量分数的高熔点高活性的四苯基氯化鏻(TPPC)与聚偏氟乙烯(PVDF)混合,探究了TPPC对PVDF极性相的诱导作用,并研究了此体系与熔体结晶过程最为相近的非等温结晶过程。结果表明,添加极少量(0.4%)的TPPC即可以使PVDF直接从熔体中全部以极性相结晶,这归因于TPPC固体表面的电荷与PVDF分子链之间强烈的相互作用。TPPC的加入使PVDF的非等温结晶行为发生了很大的变化,当TPPC含量达到0.4%时,降温结晶曲线出现两个结晶峰,也是这种反常的结晶行为才能使PVDF几乎全部以极性相结晶。     

成核剂对不同特性粘数PET结晶性能的影响

研究了新型复合成核剂水滑石(HT)／离聚物(Surlyn8920)／聚乙二醇(PEG)对不同特性粘数聚对苯二甲酸乙二醇酯(PET)非等温结晶性能的影响。通过差示扫描量热仪测试了PET的结晶峰温度T_(mc)和熔融峰温度(T_m)。结果表明,复合成核剂各组分及PET的质量比为0.5:3.0:3.0:100.0时,各种PET的过冷度(T_m-T_(mc))均显著减少．半结晶时间(1gt_(1／2))也明显降低。而且,复合成核剂对不同特性粘数PET结晶性能的改善是一致的。     

Real time in situ X-ray diffraction studies on the melting memory effect in the crystallization of β-isotactic polypropylene

The melting memory effect during the crystallization and heating of semi-crystalline polymers was clearly demonstrated using β-isotactic polypropylene (β-iPP). Differential scanning calorimetry and real-time in situ X-ray diffraction using a synchrotron radiation source were employed to investigate the role of the newly formed α-form crystals via phase transformation from the metastable β-form during the melting process, and to elucidate the memory effect of these new α-form crystals during the crystallization process. The evolution of the memory effect in β-iPP during the crystallization and melting processes is ideally based on the existence of locally ordered α-form in the melt. We monitored the role of this local order by preparing the melt state using a range of hold temperatures and hold times. It was found that the final melt temperature and hold time greatly affect the crystallization behavior during cooling and the phase transformation behavior during heating. Lower hold temperatures and shorter hold times lead to samples rich in α-modification, whereas longer hold times generate samples rich in β-modification during crystallization. At higher hold temperatures even a short hold time is sufficient to destroy the local order in the melt, and the resulting sample exhibits more β-modification. The results are explained on the basis of the existence of local order in the amorphous melt along with external nucleating agent during the crystallization process.     

Crystallization of X-ray amorphous Ca-Mg aluminosilicate materials

The crystallization mechanism has been considered for amorphous materials prepared by cooling silicate melts of the batches based on dunite and limestone, as well as those based on MgO, CaO, and SiO₂, after deep reducing melting and the removal of the iron-containing metallic moiety from the melt. The specific features in the nucleation of centers generating a heat wave of self-propagating crystallization are revealed, and the possibility of visualizing these centers is demonstrated. The values of crystallization heats released in the process and changes in temperature of the heat wave front are reported, and the rate of the wave front propagation is determined.     

MINLP‐Optimierung des Hybridverfahrens Destillation/Schmelzkristallisation

The hybrid separation process distillation/melt crystallization offers a cost wise attractive alternative compared to conventional distillation processes. In this work, the systematic and cost optimal design of this combination process is considered. The focus is on the optimal choice of operating and structural degrees of freedom.     

Hybrid separation processes combining vacuum distillation with fractional crystallization,partial melting,and granulation

The physicochemical fundamentals of the combined processes of distillative crystallization (also called distillation crystallization or distillative freezing) and distillative sweating (also called distillation sweating or distillation melting) are considered. Results of the experimental study of the kinetics of separation of binary and ternary organic mixtures of various forms (liquids, powders, continuous layers, and granules) are presented. The high efficiency of the combined processes that make it possible to rapidly decrease the impurity content by one to two orders of magnitude after a single stage is shown. It is found that these processes can be used for effective separation of the mixtures of a eutectic composition when conventional crystallization is not applicable. Dependences of the important kinetic characteristic—an effective diffusion coefficient—on pressure are determined for a number of mixtures. An empirical formula for estimating its values is proposed. It is found that the kinetic features of the combined processes conducted under nonequilibrium conditions can cause both a decrease and an increase in the efficiency of separation of the mixtures of different types in comparison with calculated values for the equilibrium process. A method is developed that makes it possible to combine distillative crystallization with the granulation of a melt in a semicontinuous or continuous process on a cooled movable belt. The method ensures the additional purification of solidifying granules from volatile impurities. Results of calculating the main characteristics of the combined process for purifying naphthalene granules in the batch and continuous modes are given.     

Application of functionalized magnetic silica nanoparticles for selective induction of three coumarin metastable polymorphs

The precise control of active pharmaceutical ingredient (API) crystal nucleation and polymorphism is a key consideration in pharmaceutical manufacturing. In this study, tunable nanoparticles were developed to regulate the nucleation process of coumarin. Magnetic silica nanoparticles with four different functional groups (—NH₂, —COOH, —SH, —NCO) were prepared and coated on the substrate for inducing the crystallization of coumarin. Confined melt crystallization and microspacing sublimation crystallization methods were used to investigate the regulation mechanism. The results indicated that three metastable forms of coumarin can be obtained as pure components based on the combined influence of crystallization methods and functionalized nanoparticles. Form II could be selectively obtained by microspacing sublimation crystallization on Fe₃O₄@SiO₂—SH substrates, and Form IV could be obtained by confined melt crystallization on Fe₃O₄@SiO₂—NCO substrates. Form III could be obtained by further heating Form IV crystals to 52 ℃ on Fe₃O₄@SiO₂—NCO substrates. Moreover, the polarized light microscopy results also indicated that the introduction of nanoparticles could also increase the stability of the metastable crystalline forms of coumarin. Finally, the diffusion and surface dynamics during nanoparticle induced crystallization were comparatively investigated and the corresponding polymorphic selectivity mechanism was proposed.     

Speculations on a New Mechanism of Crystal Growth from Aqueous Solutions

The activity of lead ions to form heterogeneous nuclei in supersaturated KCl solutions was shown (in previous publications) to account quantitatively for the effect of these ions on the limit of stability of the supersaturated solutions, the rate of crystallization, and the co-precipitation of the lead ions with the crystallizing salt. Hence the process of crystal growth is described as the deposition of subcolloidal sized nuclei on the crystal seed. Many otherwise perplexing phenomena recorded in the literature, and observed in studies of various aspects related to the crystallization of KCl and NaCl, prove to be a direct consequence of this mechanism of crystallization. Other examples indicate that heteronucleation and a similar growth mechanism may be prevalent in the crystallization of several salts from their aqueous solutions. Some implications and possible applications of the proposed growth mechanism are also discussed.     

Thermal properties and non‐isothermal crystallization behavior of poly(trimethylene terephthalate)/poly(lactic acid) blends

Thermal properties and non‐isothermal melt‐crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(lactic acid) (PLA) blends were investigated using differential scanning calorimetry and thermogravimetric analysis. The blends exhibit single and composition‐dependent glass transition temperature, cold crystallization temperature (T_cc) and melt crystallization peak temperature (T_mc) over the entire composition range, implying miscibility between the PLA and PTT components. The T_cc values of PTT/PLA blends increase, while the T_mc values decrease with increasing PLA content, suggesting that the cold crystallization and melt crystallization of PTT are retarded by the addition of PLA. The modified Avrami model is satisfactory in describing the non‐isothermal melt crystallization of the blends, whereas the Ozawa method is not applicable to the blends. The estimated Avrami exponent of the PTT/PLA blends ranges from 3.25 to 4.11, implying that the non‐isothermal crystallization follows a spherulitic‐like crystal growth combined with a complicated growth form. The PTT/PLA blends generally exhibit inferior crystallization rate and superior activation energy compared to pure PTT at the same cooling rate. The greater the PLA content in the PTT/PLA blends, the lower the crystallization rate and the higher the activation energy. Moreover, the introduction of PTT into PLA leads to an increase in the thermal stability behavior of the resulting PTT/PLA blends. Copyright © 2011 Society of Chemical Industry