退火温度和时间对PET高卷速拉伸变形丝熔化与结晶行为的影响

本文用DSC和密度法研究了高卷速拉伸变形丝(DTY)的熔化与结晶行为。定量地测定了不同温度迟火5分钟急冷后的试样,在DSC曲线上出现的各转变峰温和热焓随退火温度变化的规律,找到了DSC测定的熔化热焓和密度法测定的结晶度之间的对应关系。从试样在熔化峰温退火→冷却结晶→再扫描和在熔化峰温→继续扫描两种方式在DSC曲线上所表现的熔化与结晶行为,探讨了试样在熔融状态退火冷却结晶后再扫描出现双熔化峰的原因,继而研究了试样在熔化峰温的退火时间对结晶完善程制的影响。     

半结晶聚合物的多重熔化行为

<正> 半结晶聚合物双重熔化行为研究历史经过拉伸取向、退火、或沉淀的半结晶聚合物常常在具差热分析(DTA)、差示扫描量热(DSC)曲线上出现双重熔化峰。从五十年代以来不断出现有关双重熔化峰产生原因的研究报导。1955年White在拉伸取向的尼龙66、尼龙6、尼龙11、聚胺酯的DTA曲线上,首次观察到双重熔化峰,他将低温峰归因于取向晶体的解取向吸热,将高温峰归因于晶区的熔化。Bell在早期研究拉伸的退火的尼龙66、聚对苯二甲酸乙二酯(PET)     

热处理对尼龙1010固态结晶和玻璃态热松驰的影响

本文用DSC首先论证淬火尼龙1010试样在DSC曲线上出现的放热峰是冷结晶峰,然后研究淬火尼龙1010在不同热处理条件下,冷结晶峰和玻璃态热松驰峰的变化规律。实验结果表明,等温结晶时间较短,试样的固态结晶速率较快;等温结晶时间较长,固态结晶速率较慢,这可能与在Tg区域等温所形成的新氢键有关。当升高等温温度时,固态结晶速率加快。在低于Tg的不同温度退火,玻璃态热松弛峰的峰高及热焓在281K达最大值,进而确定对玻璃态热松驰影响最敏感的温度区间是277～284K。     

尼龙1010在加热扫描中结构重组的研究

用DSC观察了经不同热处理的尼龙1010的热历史和结构重组的再现过程。合理地解释了DSC曲线上吸热和放热峰的性质,提出预熔结晶峰表征再结晶集合的观点。确定了对结晶完善敏感的热处理温度范围。为尼龙1010的加工和应用提供了部分理论依据。     

尼龙1010经逐步降温退火形成的晶体的热稳定性

本文用DSC研究了尼龙1010在低于其熔点下进行逐步降温热处理后的熔化行为及其由热处理所形成的晶体的热稳定性。实验结果表明,尼龙1010经逐步降温热处理后可产生与之相应步数的熔化峰,直观地反映了试样的热历史记忆,从而说明逐步降温热处理能够产生各自独立熔化的晶体。这些晶体在低于其热处理温度下是稳定的。     

固态缩聚尼龙1010的熔化行为

本工作借助示差扫描量热法和X-射线衍射分析法(WAXD)首次研究了固态缩聚反应所得初生态尼龙1010的结晶特征和熔化行为。实验结果表明:固态缩聚反应的温度和时间以及产物分子量对初生态尼龙1010的熔化行为有着明显的影响。初生态尼龙1010结晶熔融双峰的显隐与其X-射线衍射峰特征没有明显的依赖关系,但随着尼龙大分子结晶的完善化而出现表观体积收缩观象。     

聚对苯二甲酸丁二醇酯的多重熔化及其平衡熔点的测定

本文用差示扫描量热法(DSC)通过改变在松弛状态下的热处理条件,观察了PBT树脂的多重熔化行为,认为该材料的多重熔化行为符合“结构再组合”的观点。并测定了它的平衡熔点。     

尼龙1010在熔融峰温等温结晶生成晶体的热性质和形态结构

用 DSC,TEM,ED 研究了尼龙1010在熔融峰温等温结晶生成晶体的热性质和形态结构。结果表明该晶体在 DSC 扫描的时间尺度范围内是稳定的,能保持原有的熔融特性,不是低熔点晶体转化而成的晶体。对该晶体进行电子衍射,显示对称的清晰的单晶电子衍射斑点,用尼龙1010的晶胞参数标定电子衍射图,证明是单晶的电子衍射图。     

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℃.     

用 DSC 鉴定高分子材料组成的研究

本文用DSC研究了标致汽车保险杆的组成。研究了试样从熔体淬火,加热速率,冷却速率,部分扫描,部分扫描→等温扫描对DSC曲线的影响,从而确定试样是两种高分子材料的共混物。经用Barta的添加热分析法鉴别,证实是聚丙烯和高密度聚乙烯的共混物,然后用红外光谱予以佐证。建立了用DSC确定高分子材料组成的一套方法。     

MULTIPLE MELTING IN NYLON 1010

Multiple melting behavior of nylon 1010 has been investigated by using DSC instrument. Effects of partial scanning, partial scanning and annealing, heating rate, cooling rate and stepwise annealing on the melting curve were studied. Experimental results indicate that the sample undergoes a process of continuous melting and recrystallization during DSC scanning. Nylon 1010 contains a distribution of crystallites of different degrees of perfection which is strongly dependent on its previous thermal history. From the structural reorganization point of view, the origin of double and multiple peaks of the melting curve is explained.     

Studies of structural reorganization in Nylon 1010 during heating scanning

The process of structural reorganization and thermal history recurrence in Nylon 1010 were studied by using DSC through different heat treatments. The characteristics of both endothermic and exothermic peaks on DSC curve is explained reasonably. The viewpoint is advanced that crystallites assembly is characterized by premelting crystallisation peak. The temperature range sensitive to the crystal perfection is determined. The results provide theoretical basis for the processing and application of Nylon 1010.

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Zusammenfassung Mittels DSC bei verschiedenen Wärmebehandlungen wurde der Vorgang der strukturellen Rückordnung und das thermische Vorleben von Nylon 1010 untersucht. Sowohl exotherme als auch endotherme Peaks an der DSC-Kurve konnten plausibel erklärt werden. Das Kristallitgefüge wird durch einen Premelting Kristallisationspeak bestimmt. Der für die Kristallvollkommenheit ausschlaggebende Temperaturbereich wurde bestimmt. Die Ergebnisse liefern eine theoretische Grundlage für den Umgang und die Anwendungen von Nylon 1010.

     

Thermal properties and morphology of crystal in nylon 1010 formed isothermally at melting peak temperature

Thermal properties and morphology of crystal in NYLON 1010 formed isothermally at melting peak temperature were studied by using DSC, TEM and ED. It turns out that the crystal on the time scale of the DSC experiment is stable, which is not transformed from the crystal with low melting point. Its electron diffraction pattern shows symmetrical and clear electron diffraction spots of single crystal and is proved to be the electron diffraction pattern of single crystal by means of index with parameters of unit cell of Nylon 1010     

Isothermal crystallisation kinetics of poly(3-hydroxybutyrate) using step-scan DSC

The crystallisation kinetics, melting behaviour and morphology, of bacterial poly(3-hydoxybutyrate) (PHB) have been investigated by using differential scanning calorimetry (DSC), step-scan DSC (SDSC), wide angle X-ray diffraction (WAXRD) and hot stage polarised optical microscopy (HSPOM). DSC imparted isothermal crystallisation thermal history. The subsequent melting behaviour revealed that all PHB materials experienced secondary crystallisation during heating and the extent of secondary crystallisation varied depending on the crystallisation temperature. PHB samples were found to exhibit double melting behaviour due to melting of SDSC scan-induced secondary crystals, while considerable secondary crystallisation or annealing took place under the modulated heating conditions. The overall melting behaviour was rationalised in terms of recrystallisation and/or annealing of crystals. Interestingly, the PHB materials analysed by SDSC showed a broad exotherm before the melting peak in the non-reversing curve and a multiple melting peak reversing curve, verifying that the melting-recrystallisation and remelting process was operative. HSOM studies supported the conclusions from DSC that the radial growth rate of the PHB spherulites was significantly varied upon the crystallisation conditions. One form of crystals was shown by WAXRD from isothermally crystallised PHB.     

DSC 曲线解析

本文以作者发表的论文为基础阐述了解析DSC曲线应具备的理论知识和技能,并以作者解析抗癌药倍半氧化羧乙基锗、尼龙1010、标致汽车保险杆的DSC曲线为例,说明作者解析DSC曲线的思路和方法。     

Melting of constrained drawn nylon 6 yarns

A differential scanning calorimeter (DSC) was used to study the melting behavior of drawn nylon 6 yarns which were prevented from shrinking during heating. The DSC curves exhibit a single melting peak at a higher temperature instead of the double peaks which, as reported previously, were observed in the unconstrained state. The curve is explained quantitatively in terms of the perfecting of the original crystals followed by monotonic melting of these crystals during heating. The single peak results from the absence of the partial melting–recrystallization process which plays an important role in the appearance of double peaks. The temperature of the melting peak for the constrained sample increases linearly with draw ratio, and is unaffected by drawing temperature and by annealing at constant length after drawing. The elevation of the melting temperature is discussed on the basis of the entropy effects predicted theoretically by Zachmann. Thermal analysis of constrained samples has proved to be useful for detecting oriented crystals which coexist with unoriented ones.     

DSC investigation of an isothermal crystallized poly(ethylene terephthalate)

Two samples of poly(ethylene terephthalate), oriented and unoriented (annealed for several times and temperatures), were scanned by DSC. The density of the samples was also determined. A thermal process was observed in the region between the glass transition and the melting temperature. The position of this thermal process is related to the annealing temperature. The model of the process was proposed as a simultaneous partial melting and recrystallization. The shape of the heating curve depends on the rate of both processes.