原位聚合尼龙11/石墨烯氧化物纳米复合材料的等温结晶和熔融行为

采用原位聚合法制备了尼龙11/石墨烯氧化物纳米复合材料,并利用差示扫描量热分析仪(DSC)研究了材料的等温结晶动力学和熔融行为。研究结果表明,Avrami方程能够较好地描述尼龙11及其纳米复合材料的等温结晶动力学;尼龙11结晶速率受晶体生长速率控制,而纳米复合材料的结晶速率在不同的结晶温度范围内分别受晶体生长速率或成核速率控制;与纯尼龙11相比较,复合材料具有较低的平衡熔点和表面折叠自由能。     

Crystallization of partially miscible linear low-density polyethylene/poly(ethylene-co-vinylacetate) blends

Miscibility and crystallization of linear low-density polyethylene (LLDPE)/poly(ethylene-co-vinylacetate) (EVA) blends were investigated by optical microscopy (OM) and differential scanning calorimetry (DSC). It was found that there existed liquid–liquid phase separation (LLPS) below 220 °C over the whole composition. However, the depression in the crystallization temperature, melting temperature and equilibrium melting temperature of LLDPE all indicated that this polymer pair was partially miscible. The crystallization and melting behavior of LLDPE were determined by the dilute effect of non-crystalline EVA and the probable co-crystallization of parts of EVA chains with LLDPE chains. The crystallization and melting behavior of EVA was determined by the competence between a nucleation effect of LLDPE crystals and partial miscibility between this polymer pair, which was different from that of LLDPE.     

Atomistic simulations of spinodal phase separation preceding polymer crystallization

Many polymeric materials crystallize when cooled below their melting temperature. Although progress has been made in our understanding of the crystallization process through both experimental and theoretical efforts, these studies have focused mainly on the crystal nucleation and growth mechanism, where critical nuclei are formed from a metastable state during the first stages of crystallization, leading ultimately to the growth of crystal domains. Attention has also been given to the structure during the precrystallization (induction period). A pretransition state occurring before crystallization has been characterized as an unstable phase separation initiated by density and orientational fluctuations. These fluctuations are caused by an increase in the average length of rigid trans segments along the polymer backbone during the induction period. These observations are consistent with the theory proposed in ref. 14 on the isotropic-to-nematic transition of polymer liquid crystals, that is, the parallel ordering of polymers is caused by an increase in chain rigidity. Here we use large-scale computer simulations to investigate melts of polymers in the early ordering stages (induction period) before crystallization. In the ordered domains we identify growing dense regions similar to smectic liquid crystals. Our simulations reveal a 'coexistence period' in the ordering before crystallization, where nucleation and growth mechanisms coexist with a phase-separation mechanism.     

聚羟基丁酸酯的等温与非等温结晶动力学

用差示扫描量热法(DSC)研究了聚羟基丁酸酯(PHB)的等温与非等温结晶动力学。采用Avrami方程分析了等温结晶动力学,Avrami指数n≈2,表明PHB以异相成核的二维平面晶体方式生长,等温结晶活化能为82.4 kJ/min。采用Jeziorny法和莫志深法分析了PHB的非等温结晶动力学,Avrami指数n≈3,表明PHB非等温结晶过程以异相成核的三维球晶方式生长。     

Function space theory of dynamic nucleation during solidification at high cooling rates

An analytical theory is proposed to study the dynamic nucleation of crystals from melt at very high cooling rates (10⁻⁶ to 10⁻¹² °K/sec). The mathematical framework is found to be isomorphic with the function space theory, wave and matrix mechanics, which enables application of various approximate methods of the latter disciplines. In principle, the mathematical apparatus and concepts of function space and wave mechanics can be utilized to study the time varying nucleation process. The Arrhenius law has been used to extrapolate the self-diffusion coefficient as a function of temperature above the melting point than those below. Since, applicability of Arrhenius equation at very high degrees of supercooling is not known and has to be substituted with appropriate constitutive relationship based on free volume theory of transport, the conclusion derived from the present analysis will not be unique with respect to the certainty of crystallization during the solidification process.     

过氧化物动态硫化EPDM/PP热塑性弹性体的等温结晶行为

通过差示扫描量热分析法详细表征了PP、PP/过氧化物、EPDM/PP及过氧化物动态硫化EPDM/PP(TPV)的等温结晶行为。结果表明,与EPDM的简单共混既降低了PP的结晶速率也降低了PP的结晶度,过氧化物动态硫化后交联的EPDM颗粒作为异相成核剂,能大大提高PP的结晶速率但也严重地降低了PP的结晶度,TPV的Avrami指数为3.5,符合异相成核的三维球型生长方式。X射线衍射结果表明,4组样品的晶体结构完全相同,仍为α型单斜晶体。熔融曲线显示过氧化物/PP及TPV相比PP,在153℃出现额外熔融峰,PP原有的160℃熔融峰逐渐消失而153℃熔融峰强度逐渐增强且体系的结晶度逐渐降低。采用移动窗口二位相关红外对TPV熔融行为进行研究,发现153℃处的熔融峰对应于10个和5个单体单元螺旋序列结构,160℃时对应12个单体单元螺旋序列结构。较低的结晶温度有助于长螺旋序列结构的形成及PP结晶度的提高。     

Crystallization and morphology of a bacterial thermoplastic: poly-3-hydroxybutyrate

This paper presents a number of interesting results on the physical properties of poly-3-hydroxybutyrate (PHB). Data are presented on crystallization kinetics, morphology of melt- and solution-crystallized PHB, the variation of lamellar thickness with crystallization temperature, and the assessment of some thermodynamic quantities. These properties include surface free energies, heat of fusion and melting, and glass transition temperatures. It is shown that the special properties of PHB such as the large spherulite size, which is probably due to its exceptional purity, make it an ideal material for model studies of polymer crystallization and morphology. For example, we show that the variation of growth rate with crystallization temperature is consistent with the very latest theories; and that the single crystal morphology has important implications for the understanding of crystal growth in other polymer systems.     

MgO-Al2O3-SiO2系堇青石微晶玻璃的制备及性能研究

采用高温熔融法制备了MgO-Al2O3-SiO2系堇青石微晶玻璃,采用DTA、XRD等对试样的热处理工艺和力学性能进行了分析,详细讨论了晶化温度、晶化时间、核化温度及核化时间对该系微晶玻璃力学性能及显微结构的影响。结果表明,对于实验研究的MgO-Al2O3-SiO2系玻璃,于600℃核化处理4h,于1100℃晶化处理2h,可以得到具有较好性能的堇青石基微晶玻璃,其抗弯强度可达182MPa。     

官能团化聚丙烯改性Mg(OH)2/PP中PP结晶的异相成核作用

用DSC研究了外加官能团化聚烯烃(FPP)、接枝单体和原位形成FPP改性Mg(OH)2／聚丙烯中的异相成核作用。Mg(OH)2表面的异相成核作用使聚丙烯(PP)结晶温度提高;外加FPP使PP结晶温度进一步提高,接枝单体加入也使复合材料中PP结晶温度提高,但原位形成FPP使PP结晶温度、熔点和结晶度降低。认为在改性复合材料中存在Mg(OH)2表面异相成核作用和FPP活化Mg(OH)2表面异相成核的协同作用。     

Nucleation behaviour of poly-3-hydroxy-butyrate

Poly-3-hydroxy-butyrate (PHB) is a thermoplastic polyester produced by bacterial fermentation. Because of this bacterial origin PHB is a very pure polymer. This high purity in turn leads to very few (if any) heterogeneous nuclei, which gives a much wider scope for a systematic study of nucleation behaviour and the effect of nucleating agents than was possible before. It is shown that in pure PHB nucleation is sporadic. The nucleation rate may be measured over a temperature range of some 100° C. The nucleation rate data are recorded in the range where homogeneous nucleation is possible and are at least consistent with it. When foreign particles are added the nucleation rate is modified. Two distinct types of behaviour are observed. One may be interpreted quantitatively as the local raising of the crystal melting point due to the constraints of the actual presence of a surface; and the other as being due to epitaxial growth on the foreign surface. Detailed kinetic data are presented to support these conclusions.     

Density and crystallinity of poly (3-hydroxybutyrate/3-hydroxyvalerate) copolymers

Bacteria can produce a range of optically active copolymers of (R)-3-hydroxybutyrate (HB) and (R)-3-hydroxyvalerate (HV). These copolymers have aroused much scientific interest because of their high crystallinity at all HB ∶ HV compositions which suggests the possibility of inclusion of HB and HV in the same crystal. In this paper we look at the assessment of crystallinity by density measurements taking into account the possible changes in crystal and amorphous densities caused by the rejection or inclusion of HV from the crystallites. The approach developed is applicable to crystallization of copolymers and blends whatever the composition of the crystals and makes a distinction between mass fraction and mole fraction crystallinities for cases where the average molar mass of residues in the crystal and amorphous phases differs. While it is impossible to give values for crystallinity without knowing the degree of inclusion of HV into the crystals it is possible to say that the previous suggestions that the crystallinity remains constant independent of HV content and that there is equal concentration of HV in the crystal and amorphous phases are incompatible with the measured sample densities. We also show that the crystallization temperature is an important factor in the balance between the crystallinity and HV content of crystals.     

Isothermal crystallization kinetics and morphology of biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

Isothermal crystallization kinetics and morphology of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] with different 4-hydroxybutyrate (4HB) molar fraction were investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). The results show that the crystallization mechanism and crystal structure of P(3HB-co-4HB) copolymers are the similar as those of poly(3-hydroxybutyrate) (PHB). While the equilibrium melting point and crystallization rate decrease with the increase of 4HB molar fraction. Banded spherulites are observed in neat PHB and P(3HB-co-4HB) copolymers, and morphology is influenced apparently by the crystallization temperature and 4HB unit.     

熔融温度对PP中成核剂的异相成核作用的影响

用DSC研究了熔融温度对不同类型成核剂成核PP的异相成核作用的稳定性的影响。观察到随熔融温度提高，纯PP的成核作用稳定，降温结晶温度基本不变。而有机磷酸盐类成核剂成核PP的结果温度比纯PP的高，而且异相成核作用受熔融温度的影响也很小。但山梨醇类成核剂成核PP的异相成核作用随熔融温度提高，结晶温度逐步降低明显，表明其异相成核作用对热不稳定。     

Compositional study and cytotoxicity of biodegradable poly(ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] and poly(ethylene glycol)

Biodegradable PHB–PEG multi-block polyurethane copolymers comprising PHB blocks (M_n: 1100, 1740 and 3240) and PEG blocks (M_n: 1960, 3250, 4150 or 7950) were synthesized followed by characterization by GPC, ¹H NMR, and FT-IR. The PHB contents ranged from 9 to 62% by weight. The copolymers displayed improved thermal stabilities compared with their respective precursors. The morphological structures of the copolymers were studied by FT-IR, DSC and XRD. FT-IR revealed the existence of amorphous and crystalline phases of PHB. Both DSC and XRD analyses showed that separate crystalline phases are formed by PEG and PHB blocks in the copolymers. Upon annealing, the melting transition temperature (T_m), melting enthalpy (ΔH_m) and the fractional crystallinity (X_c) of the PEG block increased when the length of PEG incorporated into the copolymer increased. These values were higher when the PHB block length is shorter as the shorter PHB chain does not disrupt the crystallization of PEG as much as the longer PHB chain. A similar disruptive effect on the crystallization of PHB segments was observed by varying PEG chain lengths but the effect is less pronounced compared with the PEG segments. A comparison of the swelling properties of the poly(ester urethane)s showed that the length and crystalline properties of the PHB block significantly affects the water uptake properties of the copolymers. The crystalline properties and the water uptake capacities of the copolymers could be fine-tuned by consideration of the length of the PHB and PEG block incorporated. The results of the cytotoxicity tests demonstrated that the poly(PHB/PEG) urethanes were non-cytotoxic and could potentially be used for biomedical purposes.     

Tetragonal → twinned hexagonal crystal phase transformation in polybutene-1

The spontaneous transformation of the metastable (Form II) tetragonal crystals into the stable twinned hexagonal (Form I) crystals in polybutene-1 was studied using several techniques. The mechanical properties of the heat moulded material undergo significant changes in the process and the crystalline melting point increases from 112 to 128‡ C. Results from an Avrami analysis suggest the nucleation of the stable crystalline phase occurs shortly after crystallization from the melt and the subsequent growth of the nuclei follows a rod-like geometry. Transmission electron microscopy of melt-grown thin films shows that nucleation occurs at random positions within a spherulite and growth propagates along the radially oriented fibrillar crystals. As a result of multiple nucleation, each tetragonal crystal generates several twinned hexagonal crystallites with different crystallographic orientations. Besides exhibiting multiple nucleation within each individual tetragonal crystal, solution-grown single crystals also reveal twisting of the crystal lattice about thec-axis. The information obtained shows that residual stresses present in the material do not appear essential for the nucleation of the stable phase. Current concepts of the transformation mechanism are examined.     

聚酯切片结晶熔融粘结与固相缩聚工艺优化

差示扫描量热(DSC)实验研究了聚酯切片在不同的结晶温度等温结晶样品的升温熔融行为。发现结晶温度升高,结晶熔融温度升高,切片的抗粘结温度升高;固相缩聚过程是结晶与反应同时发生的过程,反应时间延长,结晶层分布变窄,结晶熔融温度升高,且逐渐与升温熔融峰重合在一起;多段升温反应的方式,可逐步提高熔融粘结温度,避免粘结,提高反应速度。利用这种优化的反应方式,可缩短反应时间,特别适用于固相缩聚法生产高分子量(η1.0dL/g)聚酯。     

大分子相容剂改性纳米CaCO3 / PP复合材料的非等温结晶行为

熔融混炼制备了4 种大分子相容剂改性的纳米CaCO₃ / PP 复合材料, 用DSC 和WXRD 研究了复合材料中PP 的结晶与熔融行为。结果表明, 纳米CaCO₃对PP 结晶存在异相成核作用, 并诱导PP 形成β晶。相容剂丙烯酸接枝聚丙烯( PP-g-AA) 和马来酸酐接枝聚丙烯( PP-g-MA) 也存在异相成核作用, 提高PP 结晶温度。PP-g-AA、PP-g-MA 和马来酸酐接枝乙烯2辛烯共聚物(POE-g-MA) 与纳米CaCO₃存在异相成核协同作用, 进一步提高PP 的结晶和熔融温度, PP-g-MA 和POE-g-MA 还促使纳米CaCO₃诱导PP 生成β晶。但马来酸酐接枝乙烯2醋酸乙烯酯共聚物( EVA-g-MA) 则阻碍纳米CaCO₃对PP 的异相成核作用。实验结果表明纳米CaCO₃ / PP 复合材料中PP 结晶的异相成核作用与纳米CaCO₃ / PP 界面的相互作用有关, 而纳米CaCO₃ / PP 界面的相互作用与相容剂的结构有关。      

CaCl_2/E51/尼龙6复合材料的制备与性能

通过熔融共混法制备了不同CaCl2质量分数的CaCl2/环氧树脂(E51)/尼龙6(PA6)复合材料,利用DSC、流变仪、FTIR和电子拉伸机等研究了不同CaCl2质量分数下CaCl2/E51/PA6复合材料结晶行为及其力学性能,并研究了其受限机制。力学性能结果表明,随着CaCl2质量分数的增加,CaCl2/E51/PA6复合材料拉伸强度呈现出先增大后减小的趋势,当CaCl2质量分数为3%时,复合材料拉伸强度达到最大值82.67 MPa,是纯PA6的拉伸强度(60.5 MPa)的1.366倍,而结晶行为结果表明,增加CaCl2的质量分数,CaCl2/E51/PA6复合材料的成核温度、晶体生长温度、熔融温度及玻璃化转变温度均向低温方向移动,成核密度和成核速率也逐渐减小,结晶能力下降,结晶度由原来25.22%变为9.90%。     

热处理时间对透辉石系尾矿微晶玻璃析晶及其性能的影响

使用金尾矿和铁尾矿为主要原料,采用熔融法和一步法析晶热处理制备了透辉石系尾矿微晶玻璃。将其分别在低温段720℃和高温段820℃保温,使用DSC、XRD、Raman光谱、SEM和综合力学性能仪等手段研究了保温时间对透辉石系尾矿微晶玻璃析晶过程及性能的影响。结果表明：该系微晶玻璃的主晶相为单斜结构的透辉石晶体(Mg_0.6Fe_0.2Al_0.2)Ca(Si_1.5A_l0.5)O₆(JCPDS 72-1379),晶体的生长过程包括玻璃的分相、成核和晶体生长过程。热处理温度为低温段720℃时透辉石晶体的成核温度为720℃,随着保温时间的延长透辉石晶体逐渐长大且由球状晶向枝状晶演变,透灰石晶体的析出量逐渐增加;热处理温度为高温段820℃时透辉石晶体的形貌均为尺寸较大的枝状晶,但是随着保温时间的延长透辉石晶体的形貌和尺寸变化不大。综合性能最优的热处理制度为在820℃保温45 min,制备出的微晶玻璃密度为2.97 g/cm³,抗折强度为211.0 MPa,硬度为789.0 MPa,耐酸性99.3%,耐碱性99.1%。     

Transcrystallization kinetics at the poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/hemp fibre interface

Transcrystallization of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) on hemp fibres was investigated using polarized optical microscopy. Nucleation and growth of crystals of the transcrystalline region (TCR) were measured during isothermal treatments of samples located in a hot stage. The nucleation rate, nucleation density at saturation and growth rate of the TCR, were determined at crystallization temperatures between 320 and 363 K.The growth rate of crystals in the TCR is the same as that of spherulites in the bulk. Nucleation at the hemp fibres was properly described in terms of the heterogeneous nucleation theory and the transcrystalline growth agrees with the kinetics theory of polymer crystallization. From the empirical data we determined that the interfacial free energy difference function of PHBV on hemp fibres is Δσ = 4.4 erg/cm², lower than the one in the bulk. This indicates that the substrate is not neutral but contributes to the formation of the TCR.From the intensity of the depolarization light, measured under different cooling rates, we determined the activation energies for crystallization in the bulk and transcrystallization.