纳米CaCO3/聚丙烯的结晶熔融多峰行为研究

用差示扫描量热法(DSC)研究了纳米CaCO3/PP和改性纳米CaCO3/PP的非等温和等温结晶的多熔融行为。结果表明纳米CaCO3明显提高PP的结晶温度,诱导PP形成β晶。反应性单体改性纳米CaCO3/PP的结晶温度进一步提高,但对β晶熔融峰强影响不大。而在引发剂存在下反应性单体改性的纳米CaCO3/PP,促进β晶的熔融峰强明显增强。PP出现双熔融峰与PP形成β晶或者在等温结晶时形成两种不同形态有关。结晶温度提高,双峰移向高温;纳米CaCO3/PP的高温熔融峰高比低温熔融峰的高,但改性纳米CaCO3/PP在较高结晶温度时,高温熔融峰高反而比低温熔融峰的低。延长等温结晶时间对熔融峰温影响不大。     

膨胀型阻燃聚丙烯的熔融及非等温结晶行为

将多聚磷酸铵(APP)-季戊四醇(PT)-三聚氰胺(M)体系选作膨胀型阻燃剂,研究了聚丙烯/膨胀型阻燃添加剂(PP/IFR)共混物的熔化及非等温结晶行为.从DSC获得的结果表明,IFR对PP的熔化行为影响很小,但IFR的加入导致PP/IFR共混物的结晶速率比纯PP加快, Avrami指数n和结晶速率常数Zc说明其等温结晶过程为典型的三维生长的异核球状结晶;POM和SEM分析证明,IFR影响PP球晶的尺寸,但不影响其形貌结构.     

聚烯烃/聚氧化乙烯共混体系结晶与熔化行为研究

研究了HDPE/PEO,LDPE/PEO,PP/PEO共混体系的非等温结晶与熔化行为。PEO熔体对HDPE,LDPE,PP的结晶与熔化行为几乎没有影响,而已经结晶了的HDPE,LDPE,PP对处于分散相PEO的结晶与熔化行为则有一定影响,影响程度HDPE最大,LDPE次之,PP最小。这些不相容结晶/结晶共混体系的形态结构取决于低熔点组分处于连续相或分散相、高熔点组分生成的球晶大小、多少及其分布。     

聚丙烯与聚氨酯共混物结晶的研究

本文用解偏振光强度测定(DLI)、差示扫描量热(DSC)、偏光显微镜(PLM)及激光小角散射(SALS)等方法研究了聚丙烯(PP)与聚氯酯(PU)共混物的等温结晶动力学及其结晶形态。结果表明,共混物中PP的结晶过程可由Avrami方程很好地描述;Avrami指数n及全程结晶速率常数均与组成有关。部分非晶的PU作为成核剂参与PP的结晶过程;当PU含量高于20％时,由于其聚集成较大的颗粒,而对结晶起阻碍作用,PP的球晶形态也受到破坏。     

聚丙烯接枝乙烯醇结晶性能的研究

用DSC研究了PP，PP-g-VAc和两种不同醇解率PP-g-VOH的非等温结晶行为，以Reziorny修正的Avrami方程进行了动力学分析，用偏光显微镜观察了接枝物球晶形态的变化。研究结果表明：VOH接枝链可以有效地促进PP异相成核，导致Avrami指数n随醇解率增加而降低，结晶温度显著增加，结晶热焓增加；同时，由于VOH引入支链，降低了分子链的规整性，限制了PP排入晶格的速率，致使半结晶时间t_1/2和结晶速率Z_c常数降低。试样的偏光显微镜观察表明，PP-g-VAc的醇解率增加，球晶数目增多，直径减小，完善程度降低。     

结晶条件对PA1010/6球晶形态的影响

在正交偏光显微镜(PLM)和扫描电镜(SEM)下观察了不同结晶条件下PA1010/6共聚物结晶及球晶形态.Tm-20℃恒温结晶条件下,1#、2#、3#样品PLM下可以观察到正环状球晶,但球晶尺寸逐渐减小,4#、5#、6#视野很暗,说明结晶度不高;7#、8#、9#、10#、11#样品中PA6含量占绝对优势,视野亮说明结晶度相对较高,但除9#样品外没有观察到球晶特征.Tm-10℃恒温结晶条件下,1#、2#样品PLM下可以观察到正环状球晶,而3#样品是负放射性球晶,4#、5#、6#视野很暗;7#到10#样品能观察到不规整的放射状负球晶,而11#样品观察不到球晶结构.自然降温结晶条件下,1#样品PLM下观察到混合光性放射状球晶,而2#样品视野稍暗,且球晶为带消光环的正光性球晶,3#样品视野更暗,也无球晶特征;4#、5#、6#样品视野视野仍然很暗;从7#到10#样品亮度依次增加,能观察到不规整的放射状负球晶,11#样品仍然观察不到球晶结构.SEM下对比研究7#和9#样品,表明7#样品结晶区小,而9#样品有比较大的结晶区.     

原料氧化对聚丙烯结晶形态及热熔行为的影响

本文用红外光谱、X-射线衍射、扫描电子显微镜和DSC,研究了等规聚丙烯原料粉在不同情况下氧化后,熔融结晶所得同时含有α型和β型球晶的试样的结晶形态与热熔行为的变化。发现虽然氧化方法不同,但氧化机理相同;氧化程度对β晶相对含量,α及β型球晶形态和结晶度、热熔特性等均有影响。并发现了一种β型晶的网状联系晶层新形态。     

纳米CaCO3/β-聚丙烯/短切涤纶纤维三元复合材料的结晶行为

通过挤出共混制备纳米碳酸钙/β-成核聚丙烯/短切涤纶纤维复合材料,用马来酸酐接枝聚丙烯(PP-g-MA)改善相容性.研究了材料中PP的结晶和熔融行为,用修正Jeziorny法、Ozawa法及莫志深法处理了PP的非等温结晶行为.结果表明涤纶纤维和CaCO3能够促进PP的结晶和诱导形成β晶.加入β-成核剂后可得较高β晶含量的复合材料,相容剂对β-成核剂的协同作用使得β晶含量进一步增加.莫志深法能够很好地描叙复合材料中PP的非等温结晶动力学过程,而Jeziorny法和Ozawa法分析的效果不理想.     

PVC/PP共混体系的PP结晶行为及晶态-非晶态共混体系的相态结构模型

从晶态-非晶态共混体系的晶相、非晶相相互作用出发,首次分析归纳山晶态-非晶态共混体系的8种相态结构模型。研究表明:PVC/PP共混物随着PP浓度的增加,PP的结晶度逐渐增大,结晶度随组成单调变化,而PVC/PP/CPE共混物的PP结晶度随组成变化曲线在PVC/PP/CPE=60/40/3处出现极大值,超过纯PP的结晶度,这与CPE诱导PP结晶有关。成核剂苯甲酸使共混物PP结晶度提高,晶区尺寸变小。     

改性蒙脱土复合母粒对聚丙烯结晶性能的影响

将功能化聚乙烯蜡／有机蒙脱土插层复合母粒与聚丙烯(PP)共混，制备了有机蒙脱土填充的聚丙烯．采用X-射线衍射分析、差示扫描量热等温结晶分析和非等温结晶分析方法研究了有机蒙脱土复合母粒对聚丙烯结晶性能的影响，采用阿夫拉米(Avrami)方程的Jeziorny修正法研究了聚丙烯的非等温结晶动力学．结果表明，一部分有机蒙脱土可进一步被PP插层，使层间距增大，同时有机蒙脱土复合母粒使一部分PP由α晶型转变为β晶型．有机蒙脱土复合母粒填充PP的最快结晶的温度为400K．有机蒙脱土复合母粒能有效促进PP异相成核，提高PP的结晶速率和结晶温度，但对结晶速率常数影响不大．     

Study of Spherulite Growth Rate and Morphology of Polypropylene -based Blends by Image Processing Technology

The method for measuring the spherulite growth rate and studying the morphology of polypropylene - based blends by image processing technology is described. The main advantages of this method, as compared to existing techniques, are: better reliability; reproducibility; ease of manipulation. Such an approach provides a means of measuring the rate of spherulite growth. In this study, isotactic polypropylene (PP), polystyrene (PS)/PP, and polybutylene terephthalate (PBT)/PP have been studied. The results show that the technology of image analysis is very useful in the study of the kinetics of crystallization of polymer.     

Crystallization Behavior of Copolymer Poly(ethylene terephth-alate/isophthalate)(IPET)

The non-isothermal crystallization kinetics, isothermal crystallization and the morphology of crystals of the copolymer poly ( ethylene terephthalate/ isophthalate ) (IPET) were studied by DSC and polarized-light microscopy in this paper. DSC results indicate that the glass transition temperature Tg of IPET is slightly lower than that of poly (ethylene terephthalate) (PET), but the melting temperature Tm and the crystallization temperature Tc of PET and IPET have much difference. The difference of Tc between PET and IPET2 is about 7℃, and the difference of Tm between PET and IPET2 is about 16℃. From the kinetics analysis of the crystallization, the crystallization mechanism of all samples is of three-dimension spherulitic growth from instantaneous nuclei and the incorporation of isophthalate (IPA) decreases the crystallization rate of IPET greatly. The isothermal results indicate that the morphologies of PET and IPET crystals are all spherulite, which is in conformity to the results of non-isothermal d     

POM/TPU共混合金非等温结晶动力学研究

通过布拉本德单螺杆挤出机熔融共混挤出制备聚甲醛/热塑性聚氨酯(POM/TPU)共混合金.采用差示扫描量热仪(DSC)和热台偏光显微镜(HS-PLM)对POM/TPU共混合金的非等温结晶动力学及POM球晶生长形态进行跟踪观察.结果表明:采用莫志深法对POM/TPU共混合金的非等温结晶动力学分析结果与Jeziorny法相吻合;POM结晶过程中同时存在均相成核和异相成核,TPU提高了POM的结晶完善性.     

不饱和结晶性聚酯的结晶行为研究

采用差示扫描量热仪（DSC）测试一种不饱和结晶性聚酯的熔融温度,并使用Avrami方程和Jeziorny法、Ozawa法和Mo法分别对不饱和结晶性聚酯的等温结晶动力学和非等温结晶动力学进行研究,通过偏光显微镜对不饱和结晶性聚酯等温结晶后的结晶形貌进行了观察。结果表明：不饱和结晶性聚酯的熔点受升温速率的影响;等温结晶的温度越高,结晶速率也越大;晶体形貌为球晶;结晶性聚酯存在二次结晶,且随着相对结晶度的增大,结晶变得越来越困难。由于存在二次结晶,Ozawa法和Jeziorny法均出现偏移,而Mo法用于不饱和结晶性聚酯的非等温结晶动力学分析较为合适。     

Cellulose nanocrystals as green fillers to improve crystallization and hydrophilic property of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The green nanocomposites of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with various cellulose nanocrystals (CNCs) contents were prepared by solution casting method. The effects of CNCs on the crystallization behavior, spherulitic morphology, crystal structure and hydrophilic property of PHBV were studied by differential scanning calorimeter (DSC), polarized optical microscope (POM), wide-angle X-ray diffraction (WAXD) and static water contact angle measurement. It is found that the CNCs act as an effective nucleation agent for crystallization of PHBV, inducing an increase in the melt crystallization temperature of the nanocomposites. A study of the non-isothermal crystallization kinetics further illustrated that overall crystallization rate of PHBV in the nanocomposites was faster than that of neat PHBV, but exhibited a decrease in the crystallinity and the spherulite size of PHBV. Furthermore, the contact angle decreased from 60.1° for neat PHBV to 32.5° for the nanocomposites with 10% CNCs (mass fraction).     

Cellulose nanocrystals as green fillers to improve crystallization and hydrophilic property of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The green nanocomposites of poly(3-hydroxybutyrate-co-3-hyd roxyvalerate) (PHBV) with various cellulose nanocrystals (CNCs) contents were prepared by solution casting method. Th e effects of CNCs on the crystallization behavior, spherulitic morphology, crystal structure and hydrophilic property of PHBV were studied by differential scanning calorimeter (DSC), polarized optical microscope (POM), wide-angle X-ray diffraction (WAXD) and static water contact angle measurement. It is found that the CNCs act as an effective nucleation agent for crystallization of PHBV, inducing an increase in the melt crystallization tempera ture of the nanocomposites. A study of the non-isothermal crystallizatio n kinetics further illustrated that overall crystallization rate of PHBV in the nanocomposites was faster than that of neat PHBV, but exhibited a decrease in the crystallinity and the spherulite size of PHBV. Furthermore, the contact angle decreased from 60.1° for neat PHBV to 32.5° for the nanocomposites with 10% CNCs (mass fraction).     

磁场对熔融结晶聚丙烯薄膜晶体结构的影响

采用偏光显微镜分析比较了聚丙烯在磁场作用下的熔融结晶过程·结果表明:聚合物在熔融状态下易受外磁场的作用而产生诱导偶极,结晶时与未经磁场作用的分子链有不同的构象·静磁场使聚合物球晶沿磁场方向被拉长,趋于定向结晶,在外磁场的"牵引"下,结晶区前沿形成"须状"附加结晶区,极化作用使辐射状片晶由扭曲生长变为伸直生长,消光环消失,同时静磁场对聚合物成核有抑制作用,使其成核率降低而球晶尺寸增大·交变磁场对球晶形貌无显著影响,辐射状片晶由扭曲生长变为伸直生长,消光环消失,同时交变磁场对聚合物的结晶过程有电磁搅拌作用,使成核率增高而球晶尺寸减小·