聚丙烯β相结晶的研究

本文研究了冷却速率、结晶温度和熔体温度等因素对聚丙烯β相结晶得到的试样的熔融行为的影响。发现β晶型熔融峰的面积随冷却速率的降低或结晶温度的升高而增加。在低于300℃的温度下,熔体温度对聚丙烯的β相结晶无影响。300℃以上的高温破坏了聚丙烯β相结晶的晶核,冷却结晶时不再生成β相晶体。测定了α相及β相球晶在123—140℃的温度范围内线性增长速率,发现在140℃以下,β球晶的增长速率大于α球晶。研究了β相结晶动力学,发现聚丙烯β相结晶不符合Avrami方程,而要用不完全球晶结晶的动力学理论来描述。     

填充间规聚苯乙烯的结晶

间规聚苯乙烯(sPS)性能取决于结晶行为与晶型,sPS结晶行为与形态有许多研究.本文重点综述了黏土、纳米CaCO3、滑石粉、SiO2、Mg(OH)2、TiO2,和成核剂等对sPS结晶行为、结晶形态、熔融特性与晶型的影响.认为sPS结晶行为与晶型取决于成核能垒.成核能垒低,有利于形成α-晶.熔融温度提高,提高成核能垒,有利于形成β-晶.填料加入阻碍sPS结晶成核,提高成核能垒,有利于形成β-晶.成核剂加入,降低成核能垒,有利于形成α-晶.     

β晶型聚丙烯的力学性质

研究了主要含β晶型的聚丙烯在不同温度下的应力-应变性质,并与同一商品牌号得到的α晶型聚丙烯作了对比。发现,β晶型试样的屈服强度低于α晶型,而抗冲击强度则比α晶型试样高1—2倍。结合X射线衍射法对β晶型试样在拉伸过程中发生的晶型转变的研究及形变的分子机制解释了二种晶型试样在力学性质上的差异。     

聚丙烯催化合金(PP-c)的晶体结构及其影响因素

用差示扫描量热法(DSC)和广角X射线衍射(WAXD)研究了两种乙烯含量不同的聚丙烯反应合金(PP-c)等温结晶下的晶体结构及PPβ晶含量的影响因素.结果表明,在通常的等温结晶条件下,乙烯含量较高的试样(PEP40)的熔融曲线出现双熔融峰.WAXD分析证明,其熔融双峰分别代表均聚聚丙烯(PP)的α晶和β晶.计算结果表明,PEP40中β晶含量与结晶温度有关,124℃结晶时β晶含量最高.在220℃对PP-c熔体进行热处理可显著提高PEP40中β晶的含量;在相同温度下热处理后,较低乙烯含量的试样(PEP20)也出现晶型异构.比较200℃与220℃下热处理对PEP20等温结晶的结晶形态的影响,发现后者使微晶尺寸明显变小,并呈现较完善的β球晶形态.     

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。     

由N—催化剂催化聚合的聚丙烯结晶行为研究

用小角X-射线散射法(SAXS),广角X-射线衍射法(WXAD)和差示扫描量热法(DSC)对由N-催化剂催化聚合的聚丙烯结晶行为进行探讨。发现这种聚丙烯结晶中有β晶型存在,且其含量随结晶时间增加而增加随结晶温度升高而降低;β晶含量增加,聚合物的长周期也会增加,β晶对长周期的影响比α晶更大。乙烯共聚改性后的聚丙烯因分子链规整性下降而阻止了β晶的形成。在熔融状态下结晶时,β晶的形成要求聚丙烯的分子链具有更高的规整性。这些实验结果均从分子链段结晶机理得到了解释。     

成核剂含量对β晶相聚丙烯结晶与熔融行为的影响

用DSC研究了β成核剂含量对β聚丙烯在等温与非等温结晶条件下的结晶与熔融行为的影响,发现当成核剂含量为0.005％时,结晶焓△H_c、β晶的熔融焓△H_(mβ)及熔点T_(mβ)均为最大,而α晶的相对含量最小.广角X-衍射数据表明,成核剂含量高的试样的(301)衍射峰的相对强度下降,反映分子链排列的纵向有序性降低.根据聚丙烯分子在β成核剂上附生结晶的成核机理解释了上述结果.     

β晶型成核剂N,N’-二环己基环己对二甲酰胺的合成与应用研究

合成了新型成核剂N,N’-二环己基环己对二甲酰胺(DCHCHDA),用广角X射线衍射仪、差示扫描量热仪和偏光显微镜对其进行了表征,并研究了其对等规聚丙烯(IPP)的力学性能、结晶行为、β晶含量和熔融行为的影响。结果表明,成核剂DCHCHDA主要是改变球晶的形态,可明显改善IPP的抗冲击性能,并可以大幅度提高IPP的结晶度、β晶含量与结晶峰温度。当DCHCHDA添加量为0.05(wt)%时,IPP的悬臂梁缺口抗冲击强度可以提高137%,结晶度提高47%,β晶含量提高3.3倍。当降温速率为10℃/min时,添加DCHCHDA的IPP的结晶峰温度可从空白样的115.6℃提高到127.5℃。DCHCHDA的成核性能优于传统的芳香酰胺型β晶型成核剂DC26NDCA。     

取代芳酰胺型β成核剂TMB5的形态演变规律及其对iPP的β晶诱导行为的影响

采用示差扫描量热、偏光显微镜、X-射线衍射、热重分析及红外光谱分析等手段,研究了以TMB5为代表的取代芳酰胺型β成核剂在不同加工条件下的形态演变规律及其对i PP的β诱导结晶行为的影响.结果表明,TMB5虽然没有明确的熔点,但其原始晶体可以在升温中逐渐熔融并在降温时形成较细的棒状形态;而TMB5对i PP结晶的诱导作用主要和其在i PP熔融体中产生的二次形态密切相关:在保证TMB5分解不明显的温度条件下,混炼温度的提高有利于TMB5在冷却过程中形成更为细小的棒状形态,使PP中β晶的相对含量提高;在混炼之后的二次加工成型过程中,较低的熔融温度和较慢的降温速度有利于β晶含量提高.     

稀土氧化物对聚丙烯晶型和动态力学性能的影响

本文用DSC和粘弹谱仪研究了La_2O_3,Y_2O_3和混合稀土氧化物对全同聚丙烯(iPP)的结晶行为,熔融行为和动态力学性能的影响。结果表明不同的iPP/稀土氧化物复合材料中iPP的晶型不同,Y_2O_3和稀土氧化物是iPP的α和β晶成核剂,La_2O_3是α晶成核剂。含有β晶试样同只有α晶试样相比,在T_g真松弛区其tanδ值较低,贮能模量E从-50℃～+50℃较高,从+50℃～+145℃则E值较低。     

Evaluation of the physical stability and local crystallization of amorphous terfenadine using XRD-DSC and micro-TA

It is very difficult to follow rapid changes in polymorphic transformation and crystallization and to estimate the species recrystallized from the amorphous form. The aim of this study was to clarify the structural changes of amorphous terfenadine and to evaluate the polymorphs crystallized from amorphous samples using XRD-DSC and an atomic force microscope with a thermal probe (micro-TA). Amorphous samples were prepared by grinding or rapid cooling of the melt. The rapid structural transitions of samples were followed by the XRD-DSC system. On the DSC trace of the quenched terfenadine, two exotherms were observed, while only one exothermic peak was observed in the DSC scan of a ground sample. From the in situ data obtained by the XRD-DSC system, the stable form of terfenadine was recrystallized during heating of the ground amorphous sample, whereas the metastable form was recrystallized from the quenched amorphous sample and the crystallized polymorph changed to the stable form. Obtained data suggested that recrystallized species could be related to the homogeneity of samples. When the stored sample surface was scanned by atomic force microscopy (AFM), heterogeneous crystallization was observed. By using micro-TA, melting temperatures at various points were measured, and polymorph forms I and II were crystallized in each region. The percentages of the crystallized form I stored at 120 and 135 °C were 47 and 79%, respectively. This result suggested that increasing the storage temperature increased the crystallization of form I, the stable form, confirming the temperature dependency of the crystallized form. The crystallization behavior of amorphous drug was affected by the annealing temperature. Micro-TA would be useful for detecting the inhomogeneities in polymorphs crystallized from amorphous drug.     

内应力对顺-1,4-聚丁二烯结晶的影响

本工作用线膨胀仪观察了顺-1,4-聚丁二烯(PB)生胶恒温及等速降温条件下的结晶行为,发现某些胶样在结晶前出现长度增加,而加热至结晶融化时出现长度收缩,随样品退火程度的增加所述现象逐渐减小,直至消失。本工作用含凝胶样品受外力作用后能产生内应力并生成束状结晶的模型来进行解释,其结果得到DSC的验证。     

Equilibrium Crystallization Temperature of Syndiotactic Polystyrene <Emphasis Type="Italic">γ</Emphasis> Form

The crystallization behavior of syndiotactic polystyrene (sPS) γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl's crystallization theory.On the basis of the differential scanning calorimetric results,it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness,which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization.Further temperature dependent small-angle X-ray scattering (SAXS) measurement revealed the evolution of the γ form lamellae upon heating until phase transition,involving three different regimes:lamellae stable region (25-90 ℃),melt-recrystallization region (90-185 ℃) and pre-phase transition region (185-195 ℃).As a result,recrystallization line,equilibrium recrystallization line and melting line were developed for the sPS γform crystallization process.Since the melt of γform involved a γto-α/β form phase transition,the melting line was also denoted as the phase transition line in this special case.Therefore,the equilibrium crystallization temperature and melting (phase transition)temperatures were determined at around 390 and 220 ℃ on the basis of the thermodynamic phase diagram of the sPS γform.     

Nonisothermal crystallization and melting behavior of mPE/LLDPE/LDPE ternary blends

Nonisothermal crystallization kinetics of ternary blends of the metallocence polyethylene (mPE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) were studied using DSC at various scanning rates. The Ozawa theory and a method developed by Mo were employed to describe the nonisothermal crystallization process of the two selected ternary blends. The results speak that Mo method is successful in describing the nonisothermal crystallization process of mPE/LLDPE/LDPE ternary blends, while Ozawa theory is not accurate to interpret the whole process of nonisothermal crystallization. Each ternary blend in this study shows different crystallization and melting behavior due to its different mPE content. The crystallinity of the ternary blends rises with increasing mPE content, and mPE improve the crystallization of the blends at low temperature. The crystallization activation energy of the five ternary blends that had been calculated from Vyazovkin method was increased with mPE content, indicating that the more mPE in the blends, the easier the nucleus or microcrystallites form at the primary stage of nonisothermal crystallization. LLDPE and mPE may form mixed crystals due to none separated-peaks were observed around the main melting or crystallization peak when the ternary blends were heating or cooling. The fixed small content of LDPE made little influence on the main crystallization behavior of the ternary blends and the crystallization behavior was mainly determined by the content of mPE and LLDPE.     

The effect of self-nucleation on isothermal crystallization kinetics of poly(butylene succinate) (PBS) investigated by differential fast scanning calorimetry

Differential fast scanning calorimetry (DFSC) was employed on the study of self-nucleation behavior of poly(butylene succinate) (PBS).The ultra-fast cooling ability of DFSC allows investigating the effect of self-nucleation on the isothermal crystallization kinetics over a wide temperature range.Crystallization half-time,instead of crystallization peak temperature,was used to describe the self-nucleation behavior,and the self-nucleation domain for the samples crystallized at different temperatures was determined.Due to the competition between homogenous nucleation and self-nuclei,the effect of self-nucleation was less pronounced at high supercooling than that for the sample isothermally crystallized at higher temperature.An efficiency scale to judge the efficiency of nucleating agents from the crystallization half-time was also introduced in this work.     

链缠结对聚合物结晶行为的影响

链缠结是聚合物分子链相互作用的一种形式 ,它主要影响分子链的长程运动 .自链缠结的概念被提出以来 ,人们对聚合物粘弹性、流变行为和网络平衡力学等进行了理论研究和实验验证 .然而 ,在聚合物结晶领域 ,链缠结对结晶过程的影响一直存在着很大的争论 .Flory等 [1] 认为 ,聚合物结晶时分子链根本没有足够的时间进行构象调整 ,分子链进入晶格后 ,使大量的缠结链段被挤入非晶区 ,并由此建立了聚合物结晶“插线板”模型 .Hoffman等 [2 ]根据单根分子链从过冷熔体“卷饶”到晶体前沿所需的时间进行估算 ,结果比 Flory预言的快约 3～ 5个数量级…     

Crystallization of s-polypropylene: a qualitative change in the kinetics induced by the temperature of the melt

The crystallization of syndiotactic polypropylene (sPP) can be strongly affected by the temperature of the melt prior to cooling to the crystallization temperature. We observed, for a commercial sample, a variation in the form of the crystallization isotherm that cannot be explained simply on the basis of a changing number of growing hedrites.     

嵌段共聚物PVCH-b-PE-b-PVCH的多重结晶行为

通过采用差示扫描量热仪(DSC)主要研究了结晶-非晶嵌段共聚物聚乙烯基环己烷-b-聚乙烯-聚乙烯基环己烷(PVCH-b-PE-b-PVCH)溶液结晶样品的熔融与非等温再结晶过程.探讨了溶液结晶样品中微相分离结构的形成对嵌段共聚物受限结晶的影响,并发现样品在熔融后的非等温结晶过程中出现了多重结晶峰.通过对嵌段共聚物有序、...     

Nonisothermal crystallization and melting behavior of a luminescent conjugated polymer,poly(9,9‐dihexylfluorene‐alt‐co‐2,5‐didecyloxy‐1,4‐phenylene)

The nonisothermal crystallization kinetics of a luminescent conjugated polymer, poly(9,9‐dihexylfluorene‐alt‐co‐2,5‐didecyloxy‐1,4‐phenylene) (PF6OC10) with three different molecular weights was investigated by differential scanning calorimetry under different cooling rates from the melt. With increasing molecular weight of PF6OC10, the temperature range of crystallization peak steadily became narrower and shifted to higher temperature region and the crystallization rate increased. It was found that the Ozawa method failed to describe the nonisothermal crystallization behavior of PF6OC10. Although the Avrami method did not effectively describe the nonisothermal crystallization kinetics of PF6OC10 for overall process, it was valid for describing the early stage of crystallization with an Avrami exponent n of about 3. The combined method proposed in our previous report was able to satisfactorily describe the nonisothermal crystallization behavior of PF6OC10. The crystallization activation energies determined by Kissinger, Takhor, and Augis‐Bennett models were comparable. The melting temperature of PF6OC10 increased with increasing molecular weight. For low‐molecular‐weight sample, PF6OC10 showed the characteristic of double melting phenomenon. The interval between the two melting peaks decreased with increasing molecular weight, and only one melting peak was observed for the high‐molecular‐weight sample. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 976–987, 2007     

高分子液晶态有序性对其结晶过程的影响

采用退偏振光强度法、ＳＡＬＳ和ＰＯＭ测定了高分子液晶态有序微区结构随体系温度变化的规律,并用ＤＳＣ法研究具有不同有序微区结构尺寸的液晶态的结晶过程．结果发现,高分子液晶态有序性或有序微区结构是随着体系退火温度和时间的变化而变化．同时从相应的不同有序性为起始态进行结晶时,其结晶速率明显不同．并讨论了高分子液晶态的结晶机理