取向对聚左旋乳酸/聚右旋乳酸复合物纤维结晶性能的影响

通过熔融纺丝的方法制备了PLLA/PDLA复合物初生纤维,在60℃拉伸获得高取向的牵伸纤维.采用X-ray散射为主要表征手段,结合差示扫描量热(DSC)、扫描电子显微镜(SEM)以及傅里叶变换红外光谱(FTIR)等技术,系统研究了不同初始结构的PLLA/PDLA复合物纤维在不同温度下的结晶行为,重点阐明了取向对PLA复合物纤维结晶结构的影响.结果表明,取向促进复合物纤维中立构晶的形成;将纤维升温至200℃停留3 min后,再进行降温,降温过程中,高度取向的牵伸纤维只有立构晶形成,而初生纤维则在150℃左右出现α晶,表明纤维中取向的立构晶会抑制α晶的形成.综合实验结果发现,通过低温牵伸初生纤维,然后高温(α晶熔点以上)退火,可制备出高取向且具有高立构晶含量的PLLA/PDLA复合物纤维.     

聚丙烯片晶厚度对受限空间内聚丁烯-1三方晶型形成的影响

当聚丁烯-1以小液滴的形式分散在另一种树脂基体中时,会表现出不同的成核路径,即发生“分级结晶”现象.前期研究结果表明将聚丁烯-1以≤20%的比例与聚丙烯进行共混,动力学优先的晶型Ⅱ的成核会受到抑制,使得聚丁烯-1小液滴相界面处更容易发生界面诱导成核形成三方的晶型Ⅰ’.本工作采用自成核与调控聚丙烯等温结晶温度的方法,改变了聚丙烯/聚丁烯-1界面处聚丙烯的片晶厚度,发现聚丙烯的片晶越厚,晶型Ⅰ’的结晶速率越慢,进一步证明了三方晶的形成是由界面处聚丙烯诱导得到.原位广角X射线衍射结果显示,聚丁烯-1的晶型Ⅰ’是否发生重结晶取决于体系中是否存在晶型Ⅱ晶核.纯净的晶型Ⅰ’在升温过程中会直接熔融而不会转化为晶型Ⅱ.     

间同立构聚丙烯在聚乙烯(100)晶面上的附生行为研究

利用电子显微镜的欠焦成像和电子衍射技术对间同立构聚丙烯(sPP)在高密度聚乙烯(HDPE)的(100)晶面上的结晶行为进行了研究,明场结果表明,sPP能在HDPE的(100)晶面上附生生长,形成相互交叉的草席状片晶结构,电子衍射结果证明,附生生长的sPP与HDPE的接触面为(100)晶面,sPP与HDPE的分子链方向成固定的±37.交角,说明sPP在纤维取向的HDPE基质上附生结晶不仅仅是HDPE的(110)晶面对sPP有取向成核作用,(100)HDPE晶面也可作为sPP晶体的取向成核点.     

硅灰石填充聚丙烯复合材料性能的研究

本文研究了硅灰石填充聚丙烯(含乙烯22％)复合材料的热学、广角X-射线衍射和动态力学性质。复合材料中β晶含量随硅灰石含量增高而增加。试样的熔融及结晶行为表明,所有硅灰石填充试样均含有α和β两种晶型,4个结晶熔融转变;而未填充试样只有a晶型,2个结晶熔化转变。在DSC曲线上,β晶在升温过程中转变成α晶型。硅灰石填料对聚丙烯动态力学性能的影响表明,硅灰石起到了增强剂和β晶成核剂的双重作用,填料硅灰石已进入聚丙烯的结晶相。     

等规聚丙烯β晶型向α晶型的相转变行为研究进展

等规聚丙烯(iPP)是典型的多晶型半结晶性聚合物,其常见晶型有单斜(α),三方(β),三斜(γ)以及四方或双四方(e),其中稳定性最好的α晶型和处于亚稳态的β晶型工业和经济价值较大,因此二者之间的相转变行为得到了人们的广泛关注.本文综述了近年来β→α-iPP生长相转变的研究进展.在高临界温度(141°C)和低临界温度(100°C)区间内,β-iPP生长速率高于α-iPP,而温度高于141°C,或低于100°C,由于α-iPP在动力学上占优势,β-iPP会发生向α-iPP的生长转变.但由于α-iPP是热力学上最稳定的晶型,β-iPP熔融重结晶过程也会发生β→α-iPP相转变.此外,拉伸形变过程中也会发生β→α-iPP相转变,广泛用于制备聚丙烯气体交换膜、过滤膜或锂电池隔膜等.目前对变形过程中的β→α-iPP相转变机理还存在争议,本文也对2种主要的机理进行了介绍,并对聚丙烯晶型转变行为的研究方向进行了展望.     

Fe(Ⅱ)催化水铁矿晶相转变过程中Pb的吸附与固定

厌氧状态下,游离态Fe(Ⅱ)(Fe(Ⅱ)aq)催化氧化铁晶相重组是重要的铁循环化学过程,其本质是Fe(Ⅱ)aq与结构态Fe(ⅡI)间的Fe原子交换,这一过程对稻田土壤和沉积物中重金属的环境行为产生重要影响,其影响机制有待于深入研究.本研究结果显示,Fe(Ⅱ)aq催化水铁矿晶相转变过程中,重金属离子Pb(Ⅱ)通过与Fe(Ⅱ)的竞争性吸附,降低了水铁矿表面吸附态Fe(Ⅱ)浓度,抑制了Fe(Ⅱ)aq与水铁矿中结构态Fe(ⅡI)之间的Fe原子交换,最终降低水铁矿晶相转变速率并改变水铁矿晶相转变途径.无Pb(Ⅱ)时,水铁矿最终转变为针铁矿和磁铁矿;Pb(Ⅱ)影响下,转变产物主要为纤铁矿,部分为针铁矿和磁铁矿.在水铁矿晶相转变过程中,部分吸附到氧化铁表面的Pb(Ⅱ)通过晶体包裹或Fe结构位取代,被形成的氧化铁结构化固定,从而降低了重金属Pb(Ⅱ)的活性.     

中介相态丙烯-乙烯无规共聚物在热处理过程中的结构演变

通过熔体淬冷方式制备了中介相态丙烯-乙烯无规共聚物(PPR),综合使用原位红外光谱、原位X-射线散射(WAXD/SAXS)、示差扫描量热分析(DSC)和动态机械热分析(DMA)等方法系统研究了中介相态PPR在升温过程中的微观结构演变.红外光谱研究结果表明,在连续升温过程中,中介相态PPR在30~50?C之间分子链构象发生了变化,其可能源于刚性无定形区(RAF)中部分链段构象的无序化转变,并发现在RAF中存在长度为n≤13(n为31螺旋序列中丙烯单元的个数)的螺旋序列.中介相态PPR在连续升温过程中经历了RAF中链段构象的无序化转变、中介相向α晶的转变、不完善α晶的熔融和α晶的完善化,以及α晶熔融4个转变过程.中介相向α晶的转变是一个异相成核生长过程,其结晶活化能ΔE=67.94 k J/mol.     

聚(丁二酸丁二酯-co-丁二酸丙二酯)的等温结晶行为研究

以1,4-丁二酸、1,4-丁二醇和1,3-丙二醇为原料通过直接熔融缩聚法合成了聚丁二酸丁二酯(PBS),聚丁二酸丙二酯(PPS)和聚(丁二酸丁二酯-co-丁二酸丙二酯)(PBSPS)等脂肪族聚酯.利用1H-NMR,WAXD,DSC和POM等研究了聚酯的结晶结构和结晶动力学过程等结晶行为.PBSPS的结晶晶型与PBS一致,说明只有丁二酸丁二酯(BS)单元结晶而丁二酸丙二酯(PS)单元处于无定形区.聚酯等温结晶后,在升温熔融过程中出现了多重熔融峰.分析表明多重熔融峰主要来自于聚酯升温过程中的熔融-重结晶行为.利用Avrami方程分析了聚酯的等温结晶动力学,Avrami指数n为2.2~2.8,说明聚酯等温结晶时主要以异相成核的三维生长方式进行;随着PS单元的增多,聚酯的表观结晶活化能升高,也就是说BS单元的结晶变得困难.POM观察到聚酯等温结晶时都出现了环带球晶现象,球晶形态会随着结晶温度和化学结构差异而改变.     

细旦尼龙6纤维加工过程中的晶型转化行为

通过引入富镧稀土化合物等添加剂,成功实现了细旦尼龙6纤维的熔融纺丝．考察了在纺丝卷绕成型以及牵伸过程中尼龙6纤维的晶型变化．借助XRD和FT－IR等研究手段,发现尼龙6在纺丝过程中可以生成亚稳态的B晶型晶体．这种β晶型经过沸水处理后很容易转化为α晶型,而γ晶型尼龙6经沸水处理后不发生相转变．因此可以通过沸水热处理的方法区分尼龙6的β和γ晶型．在纤维的卷绕过程中,当熔体拉伸倍数较高时,尼龙6可能产生β晶型;当熔体拉伸倍数较低时,则以γ晶型为主．在纤维的牵伸过程中,γ晶型经过β晶型中间态向α晶型相转变．上述结果对于指导改进细旦尼龙6纤维的加工工艺以及提高产品性能有指导意义．     

间规聚苯乙烯的同质多晶现象

间规聚苯乙烯具有复杂的同质多晶现象，有α，β，γ，δ四种晶型和两种介晶型。本文综述了间规聚苯乙烯的晶体结构、晶型转变以及其结晶和熔融行为等方面的研究进展。     

Phase transition of syndiotactic polypropylene in electrospun nanofibers during progressive heating

By means of high-temperature electrospinning process, syndiotactic polypropylene (sPP) nanofibers with an average diameter of 127 nm were obtained using a rotating disc as a collector. The aligned fibers were subjected to progressive heating for fiber melting. During heating, structural evolution of the sPP nanofibers was investigated in situ by means of two-dimensional wide-angle and small-angle X-ray scattering with synchrotron radiation sources. It was found that the as-spun fibers consist of the antichiral form I (9 %), mesophase (31 %), and amorphous phase (60 %), in the absence of isochiral form II. Upon heating, the mesophase started to melt and completely disappeared at 90 °C. The melting of the mesophase directly produced amorphous chains at 35–60 °C, and brought up the isochiral form II at low temperatures (60–70 °C), as well as the antichiral form I at high temperatures (70–110 °C). These events were in accordance with the DSC heating curve, which exhibited a small endotherm centered at 52 °C for the mesophase melting, followed by a shallow and broad exotherm associated with two phase-transition events, i.e., the crystal reorganization and the crystallization of supercooled liquid. The former is likely due to the solid–solid transition of meso→II phase as suggested by Lotz et al. (Macromolecules 31:9253, 1998), and the latter is relevant with crystallization of amorphous chains to develop the thermodynamic stable form I phase at high temperatures.     

Annealing induced variation of crystalline structure and mechanical properties of syndiotactic polypropylene fibers

<正>Syndiotactic polypropylene(sPP) as-spun fiber(sPP1) and drawn fiber(sPP2) were prepared by melt-spinning and melt-spinning/hot-drawing,respectively.The structure transition of the two fibers induced by annealing at different temperatures and the corresponding mechanical properties were subsequently investigated by the combination of Fourier transform infrared spectroscopy(FTIR),wide-angle X-ray diffraction(WAXD) and tensile testing.The results indicate that the chain conformation and crystal forms of the two sPP fibers are not obviously changed at low annealing temperature (40℃).With increasing the annealing temperature,the trans-planar conformation and mesophase in sPP1 and sPP2 fibers can be completely transformed to helical conformation and crystal form I under tension.Upon removing the tension,a small amount of mesophase and trans-planar conformation will be regained.The mechanical properties of the annealed fibers are manifestly dependent on their initial structure and the annealing temperature.     

热历史对尼龙1212熔融行为的影响

利用DSC方法研究了不同热历史条件对尼龙1212熔融行为的影响.不同的热历史条件下,在DSC曲线上,观察到尼龙1212产生2个或3个熔融峰,依据聚合物结晶理论,对各峰的来源进行了分析.在160℃下不同温度退火120 min的尼龙1212样品DSC曲线上,低温结晶熔融峰主要由低温结晶形成的一些微晶体或者片晶熔融产生,其晶体完善程度较差,熔融峰值较低,峰面积较小;主熔融峰是由样品在淬火过程中形成的晶体和升温过程中低温结晶形成的晶体的熔融重结晶形成较为完善的晶体熔融所产生,熔融峰值较高,峰面积较大.在不同的升温速率条件下,熔融峰温度有所移动,表明不同升温速率条件下产生的熔融峰的结晶晶型是相同的.在不同结晶时间下结晶,延长结晶时间对较高完善程度晶体的生长有利.在不同温度下依次退火处理的样品,熔融产生两个附加峰,这两个附加峰的峰温都比它们相应的退火温度高,而峰高和峰面积随退火温度降低而减小.根据等温结晶结果,由Hoffman方法确定了尼龙1212的平衡熔融温度为202.8℃.     

Crystallization behavior of polyethers containing odd numbers of methylene spacers from the isotropic and liquid crystalline states

A series of thermotropic polyethers synthesized from 1-(4-hydroxyphenyl) - 2 - (2 - methyl - 4 - hydroxyphenyl) - ethane and α,ω-dibromo-n-alkanes with odd numbers of methylene units (MBPE-n = odd) shows monotropic mesophase behavior. In isothermal differential scanning calorimetry (DSC) experiments, two—sometimes even three—exothermic transition processes can be observed when the crystallization temperature is below the mesophase transition temperature, while only one exothermic process is present above the mesophase transition temperature. The melting behavior of the crystals grown from the mesophase and from the isotropic melt states is different. The crystals grown from the mesophase state exhibit a larger overall heat of transition and a higher transition temperature compared with those grown from the isotropic melt. This may be attributed to the molecular interfacial connections between the crystal and amorphous regions when MBPEs crystallize from the mesophase state. The difference in morphology between the crystals grown from the different states has also been studied with polarized light microscopy (PLM) and transmission electronic microscopy (TEM). The structures of the crystals grown from the different states are, however, the same, as evidenced through wide-angle X-ray diffraction (WAXD) measurements. From the banded morphology of MBPE samples observed from PLM, the defect textures observed through TEM and the results of WAXD experiments, this mesophase can be identified as a nematic liquid crystal state.     

The Role of the trans-Planar Mesophase in the Polymorphic Behavior of Syndiotactic Polypropylene

The transformations of the trans-planar mesophase of syndiotactic polypropylene (sPP) subjected to thermal, mechanical and solvent treatments, were investigated. The unoriented trans-planar mesophase, obtained by quenching the melt at 0°C, was annealed at 80°C and the thermal transformation was investigated by X-rays, infrared and dynamic-mechanical analysis. The presence of the helical form II was recognized in the annealed sample. The oriented trans-planar mesophase, obtained by drawing at room temperature and releasing the tension, was immersed in liquid dichloromethane for 24 hours. After drying the sample showed the presence of the oriented form II, although it was not possible to exclude a partial transition into form IV. On the basis of the present and literature results we suggested a scheme of the polymorphic transitions of sPP, in which the central role of the trans-planar mesophase is enlightened.     

Direct observation of phase transitions of polyethylene under high pressure by a PSPC x-ray system

A position-sensitive proportional counter (PSPC) x-ray measuring system is employed to observe directly phase transition processes of polyethylene at high temperature and high pressure. X-ray diffraction measurements reveal important new experimental data. First, an irreversible crystal transition from the hexagonal to the orthorhombic structures occurs in the critical region where the hexagonal structure begins to appear at a pressure of 350 MPa. That is, the (100) hexagonal reflection is observed only on cooling at 350 MPa. At pressures above about 400 MPa, however, the hexagonal phase is stable and the phase transitions melt ? hexagonal ? orthorhombic occur reversibly. Second, during cooling at pressures above 400 MPa, the (100) hexagonal reflection can be observed at temperatures below the hexagonal ? orthorhombic transition temperature. This behavior suggests that all the crystal morphologies of polyethylene, from “highly-extended-chain” crystals to crystals with a low melting point, are formed by the transitions melt → hexagonal → orthorhombic. Third, in heating at elevated pressures above 500 MPa, a shoulder in the peak intensity versus temperature plot for the (100) hexagonal reflection is observed at a higher temperature than the large maximum which occurs immediately after the crystal transition. This behavior indicates melting in two stages of hexagonal structures with different thermal stabilities, and the shoulder at higher temperature may be due to the fusion of the hexagonal phase annealed either below or above the transition point.     

Transformation of isotactic polypropylene droplets from the mesophase into the α‐phase

The structural transformation of homogeneously nucleated metastable mesophase of polypropylene (PP) particles was investigated in this study. We demonstrated the formation of heterogeneity‐free mesophase by slow cooling of the droplets unlike mesophase formation by quenching of the PP melt, which contained large number of bulk nuclei. Submicron size PP droplets were produced by thermal break up of PP and polystyrene layered film assembly. When cooled from melt, the PP droplets crystallized into mesophase at 44 °C revealing granular morphology. Subsequent heating thermogram of the PP particles showed a broad exotherm, which was attributed to the transformation of mesophase into α‐phase. This transformation was investigated during heating by annealing the PP particles at different temperatures. Annealed PP particles were analyzed by means of thermal, morphological and structural properties measurements. Results revealed a two step process for the transformation process. In the first step, the internal rearrangement of PP chains, as against melting and recrystallization of the mesophase, was observed. Since granular morphology was not affected significantly up to 120 °C, it was suggested that translational and rotational motions of PP helices produced ordered α‐phase. In the second step, increment in grain size distribution was observed, when the droplets were annealed at 140 °C. The results were attributed to enhanced chain mobility and merging of the grain boundaries. Annealing at 160 °C revealed the formation of short lamellar structures. Crystal thickening, melting and recrystallization of α‐phase were suggested at high temperature annealing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Crystalline and supermolecular structure evolution of poly(ethylene terephthalate) during isothermal crystallization and annealing treatment by means of wide and small angle X-ray investigations

Small-angle X-ray scattering, wide-angle X-ray diffraction and differential scanning calorimetry analysis were carried out to evaluate the evolution of the supermolecular structure of poly(ethylene terephthalate) (PET) during isothermal crystallization and annealing process. PET was crystallized from the melt by isothermal treatments at 226 °C. Partially crystallized samples were prepared interrupting the crystallization by quenching, while prolonged treatments were performed to prepare annealed samples. The adopted crystallization procedures allowed to form crystals which developed during primary and secondary crystallization, and the annealing process. On the basis of X-ray data, the lamellar and amorphous phases were unambiguously attributed. The lamellar thickness and the crystallinity progressively enhance with increasing the time of thermal treatment; on the contrary, the long period decreases and this effect is mainly due to the contraction of the amorphous phase. The melting behaviour of the annealed samples indicates that the heating-induced crystal reorganization phenomena are inconsistent. The interdependency between the melting temperature and the crystal thickness allowed to extrapolate the equilibrium melting temperature.     

不同后处理条件下聚萘二甲酸乙二酯纤维的结构变化

对不同纺速下制得的聚萘二甲酸乙二酯 (PEN)初生纤维进行了冷拉伸、定长热处理和热拉伸等后处理 .通过WAXS、DSC等测试研究了纤维中结构变化与后处理条件之间的关系 .结果表明 ,较低纺速下所制得的无定形初生纤维在低于Tg 温度下的冷拉伸时发生了应力诱导结晶 ,纤维中生成了α晶体 .同样的初生纤维在定长热处理过程中直至 2 0 0℃仍保持无定形结构 .这些结果说明施加应力相对于升高温度对于α晶体的生成更为重要 .而热拉伸样品中结晶结构的形成与初生纤维的结构有很大关系 ,低纺速下无定形初生纤维在热拉伸后形成α晶体 ,而高纺速下主要含有 β晶体的初生纤维经热拉伸后 β晶体会部分转变为α晶体 ,且 β晶转变为α晶的难易程度取决于初生纤维中 β晶的完善程度 ,初生纤维中 β晶越完善 ,热拉伸时 β晶体越不易转变为α晶体     

Step-scan TMDSC and high rate DSC study of the multiple melting behavior of poly(1,3-propylene terephthalate)

The multiple melting behavior of poly(1,3-propylene terephthalate) (PPT) samples after isothermal crystallization from the melt was studied. The step-scan temperature-modulated differential scanning calorimetry (TMDSC) and high rate DSC were used to investigate this behavior in conjunction with standard DSC, wide-angle X-ray diffraction (WAXD) and polarizing light microscopy (PLM). The effect of PPT average molecular weight on the melting was also examined. In general multiple endotherms after isothermal crystallization of PPT were attributed to a continuous crystal perfection process during the subsequent heating scan via melting-recrystallization-remelting. Multiple melting behavior was more pronounced for the low molecular weight PPT. Step-scan TMDSC showed that extensive recrystallization occurs in PPT samples, especially after rapid isothermal crystallization. In fact two recrystallization exothermic peaks were observed. High rate DSC revealed the initial morphology generated during the isothermal step and showed that the low and middle peaks are associated with melting of primary crystals while the high temperature peak should be attributed to melting of recrystallized material.