Detecting crystallization structure evolution of polypropylene injection‐molded bar induced by nucleating agent

The crystallization structures of Polypropylene (PP) injection‐molded bars nucleated by nucleating agent were detected from the skin layer to the core zone, layer by layer. α‐phase nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase nucleating agent aryl amides compounds (TMB‐5), and their compounds were introduced into PP matrix, respectively. The relative content of β‐phase PP in the different zones of an injection‐molded bar was characterized and calculated by Wide angle X‐ray diffraction (WAXD) and Differential scanning calorimetry (DSC). The results show that, whether in pure PP or in nucleated PP, both β‐phase PP and α‐phase PP grow in the skin layer of the injection‐molded bar. However, in the intermediate layers and the core zone, the crystallization structures of PP are dependent on the used nucleating agent. β‐phase is the main crystallization structure of TMB‐5 (0.1 and 0.2 wt%) nucleated PP, and α‐phase in DMDBS (0.1 and 0.2 wt%) nucleated PP. Compounding nucleating agents with 0.1 wt% DMDBS and 0.1 wt% TMB‐5 induces PP crystallization almost in β‐phase; however, PP nucleated by 0.2 wt% DMDBS and 0.2 wt% TMB‐5 crystallizes exclusively in α‐phase. The crystallization mechanism of PP nucleated by compounding nucleating agents was further studied in this work. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

A comparative study of polypropylene nucleated by individual and compounding nucleating agents. I. Melting and isothermal crystallization

In this study, melting and isothermal crystallization behaviors of polypropylene (PP) nucleated with different nucleating agents (NAs) have been comparatively studied. α‐phase NA 1,3 : 2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase NA aryl amides compound (TMB‐5), and their compounds were introduced into PP matrix, respectively. The crystallization and melting characteristics as well as the crystallization structures and morphologies of nucleated PP were studied by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). As indicated by previous work that a few amounts of α‐phase NA (DMDBS) or β‐phase NA (TMB‐5) has apparent nucleation effect for PP crystallization. However, the crystallization of PP nucleated with compounding NAs is dependent on the content of each NA. In the sample of PP with 0.1 wt % DMDBS and 0.1 wt % TMB‐5, the nucleation efficiency of TMB‐5 is much higher than that of DMDBS and PP crystallization is mainly nucleated by TMB‐5, and in this condition, β‐phase PP is the main crystallization structure. For the sample of PP with 0.2 wt % DMDBS and 0.2 wt % TMB‐5, 0.2 wt % DMDBS has higher nucleation efficiency than 0.2 wt % TMB5, and α‐phase is the main crystalline structure in this sample. The isothermal crystallization kinetics and crystallization structure have been analyzed in detail in this work. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synergistic toughening effects of nucleating agent and ethylene–octene copolymer on polypropylene

The synergistic toughening effect of nucleating agent (NA) and ethylene–octene copolymer (POE) on polypropylene was studied in the present work. Two different nucleating agents, such as α-form nucleating agent 1,3 : 2,4-bis (3,4-dimethylbenzylidene) sorbitol (DMDBS, Millad 3988) and β-form nucleating agent aryl amides compounds (TMB-5), were selected to blend with PP or PP/POE blends, respectively. The results show that PP containing 0.5–0.25 wt % DMDBS or 0.5–0.25 wt % TMB-5 has relatively low impact strength. For PP/POE blends, although the impact strength increases gradually with the increasing of POE content, high content of POE is needed to obtain the available PP toughness. However, once nucleating agent and POE are simultaneously added into PP, PP/POE/NA blends show great improvement of toughness even at low POE content. Furthermore, the synergistic toughening effect of POE/TMB-5 is more apparent than that of POE/DMDBS. SEM results show that whether DMDBS or TMB-5 has no apparent effect on the morphologies of POE in the PP/POE/NA blends. Further investigations using DSC and POM indicate that both DMDBS and TMB-5 induce the apparent enhancement of the crystallization temperature of PP and the sharp decrease of spherulites size of PP in the PP/POE/NA blends. The possible synergistic toughening mechanism is discussed in the work. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structural characterization of α‐ and β‐nucleated isotactic polypropylene

Modification of isotactic polypropylene (iPP) with two nucleation agents, namely 1,3:24‐bis(3,4‐dimethylobenzylideno) sorbitol (DMDBS) (α‐nucleator) and N, N′‐dicyclohexylo‐2,6‐naphthaleno dicarboxy amide (NJ) (β‐nucleator), leads to significant changes of the structure, morphology and properties. Both nucleating agents cause an increase in the crystallization temperature. The efficiency determined in a self‐nucleation test is 73.4 % for DMDBS and 55.9 % for NJ. The modification with NJ induces the creation of the hexagonal β‐form of iPP. The addition of DMDBS lowers the haze of iPP while the presence of NJ increases the haze. Copyright © 2004 Society of Chemical Industry     

Influence of a sorbitol‐based nucleating agent modified with silsesquioxanes on the non‐isothermal crystallization of isotactic polypropylene

This article investigates the effect of modifying the polypropylene (iPP) α‐phase nucleating agent 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) with tetrasilanolphenyl silsesquioxane (phPOSS). It has been proven that an increasing amount of silsesquioxane leads to differences in the crystallization behavior. What is more, it has been observed that the nucleation effect that results from the addition of sorbitol derivatives is suppressed by phPOSS activity. To understand the influence of phPOSS addition on the crystallization kinetics of PP/DMDBS/phPOSS composites that have been prepared by melt processing in a twin screw extruder, differential scanning calorimetry, rotational rheometry and Fourier transform infrared spectroscopy are performed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40131.     

DMDBS成核改性聚丙烯抗菌薄膜的研究

以二(3,4-二甲基二苄叉)山梨糖醇(DMDBS)为成核剂,油酸酰胺改性载银磷酸锆为抗菌剂,聚丙烯(PP)为基体树脂,制备了成核剂母粒、抗菌剂母粒和PP抗菌薄膜,并对PP抗菌薄膜的抗菌性能、光学性能及力学性能等进行了研究。结果表明:经DMDBS改性的PP抗菌薄膜,球晶尺寸减小,结晶密度增大,结晶温度提高;含0.2%DMDBS和0.8%改性载银磷酸锆的PP薄膜的纵、横向拉伸强度分别为49.92、33.42MPa,透光率为88.5%,雾度为3.0%,对大肠杆菌和金黄色葡萄球菌抗菌率分别为99.33%和98.35%。     

Improving crystallization behaviors of isotactic polypropylene via a new POSS‐sorbitol compound

A new compound was synthesized by chemical combination of (3‐mercapto)propyl‐heptaisobutyl polyhedral oligomeric silsesquioxane (POSS‐SH) and 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) via epichlorohydrin while hydroxyl groups were still retained in the product POSS‐DMDBS. The prepared POSS‐DMDBS was introduced into isotactic polypropylene (iPP) to improve crystallization behaviors of iPP and obtain nanocomposites with suitable mechanical properties. Crystallization and mechanical properties of iPP/POSS‐DMDBS were systematically investigated by wide‐angle X‐ray diffraction, polarization microscopy, atomic force microscopy, differential scanning calorimetry, and tensile tests. The spherulite size of the modified iPP was obviously decreased with the addition of POSS‐DMDBS, while the crystallization temperature was increased by 5°C to 9°C depending on the content of POSS‐DMDBS incorporated. POSS‐DMDBS exhibited relatively higher nucleating efficiency on iPP which is similar to that of DMDBS, confirmed by the increased crystallization temperature. It was also found that the tensile modulus of iPP after adding POSS‐DMDBS increased significantly with respect to pristine iPP, but the elongation values decreased. Introduction of POSS‐DMDBS in content less than 1 wt% could bring about effective influence on the crystallization behaviors of iPP, demonstrating its potential applications . POLYM. ENG. SCI., 57:357–364, 2017. © 2016 Society of Plastics Engineers     

Effect of continuous oscillatory shear on isothermal crystallization of non‐nucleated and nucleating‐agent‐treated isotactic polypropylene assessed by dynamic mechanical analysis

Using dynamic mechanical analysis (DMA), we investigated the in situ crystallization kinetics of non‐nucleated and nucleating‐agent‐treated isotactic polypropylene (iPP) under continuous oscillatory shear during the entire crystallization process, and then compared the DMA results with those measured using differential scanning calorimetry under conventional quiescent crystallization. Our analyses, based on the Avrami equation, show that continuous oscillatory shear accelerated crystallization of non‐nucleated iPP, but interfered with crystallization for nucleating‐agent‐treated iPP. Our results indicate that, for the present nucleating agent, its accelerating effect on crystallization cannot coexist with the accelerating effect of shear on crystallization. We attributed this difference to the disruptive effect of shear on growth and the different nucleation models of non‐nucleated and nucleating‐agent‐treated iPP. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41685.     

Polypropylene-organoclay nanocomposites containing nucleating agents

Polypropylene/organoclay nanocomposites containing nucleating agents, viz., aluminum hydroxybis[2,2-methylenebis(4,6-di-tert-butylphenyl) phosphate (NA21) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (Millad 3988), were prepared by direct melt intercalation in a twin-screw extruder. Nucleating agents were added to polypropylene during compounding and their effect on the properties of the nanocomposites was studied. X-ray diffraction (XRD) and transmission electron microscopy (TEM) exhibited clay layers to be intercalated and partially exfoliated. The expansion of inter-gallery distance of the clay layers was governed by the interaction between polypropylene, compatibilizer, and different nucleating agents. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicated higher thermal stability and crystallization temperature for nanocomposites compared to virgin polymer. Even a small addition of the nanoscale filler with 0.2% nucleating agents was found to promote concurrently several PP material properties, including improved tensile characteristics, higher Young’s modulus, increased thermal stability and rate of crystallization.     

酰胺类β成核剂对PP R非等温结晶动力学影响

研究了酰胺类β晶型成核剂对无规共聚聚丙烯(PP R)非等温结晶动力学的影响。结果表明,β成核剂提高了PP R的结晶峰温。在相同的冷却速率下,β成核剂改性PP R体系的Zc比纯PP R小,半结晶时间t1/2比纯PP R长;达到相同结晶度时,β成核剂改性PP R体系所需的冷却速率大于纯PP R,这说明β成核剂的加入降低了PP R的结晶速率。莫法可以很好地表征PP R及β成核剂改性PP R体系的非等温结晶行为。     

成核聚丙烯的研究进展

综述了近几年聚丙烯（ＰＰ）成核剂及其成核ＰＰ的结晶与熔融行为、形态、断裂韧性、降解行为、成核作用对温度的依赖性和成核机理的研究进展,讨论了成核剂对ＰＰ物理与力学性能的影响。     

PP/多壁碳纳米管复合材料的非等温结晶动力学

用超声处理溶液絮凝法制备聚丙烯(PP),多壁碳纳米管(MWNT)复合材料。扫描电子显微镜分析表明, MWNT呈纳米级分散。用Jeziomy法和MO法对材料非等温结晶差示扫描量热法结果进行动力学处理,发现复合材料的结晶峰温升高,半结晶时间减小;但随MWNT含量变化不大。复合材料的结晶速率常数比纯PP大;Avrami指数比纯PP小。要达到相同的结晶度,复合材料所需的降温速率小于纯PP。MWNT可成为PP的成核剂。     

Preparation of polypropylene/glass fiber composite with high performance through interfacial crystallization

This paper reported an approach to improve the interaction between glass fiber (GF) and polypropylene (PP) through interfacial crystallization. The experimental results showed that polar nucleating agents had strong interaction with GF and tended to deposit on the surface of GF through the dip‐coating method. Since the nucleating agents had good lattice matching with PP, the modified GF could promote the interfacial crystallization of PP to increase the interfacial interaction between GF and PP and improve the performance of PP/GF composites. However, at high processing temperature, the nucleating agents dissolved into the polymer melts, and the nucleation on the GF surface for PP crystallization decreased, impairing the interface compatibility and the final performance of the PP/GF composites. J. VINYL ADDIT. TECHNOL., 23:284–289, 2017. © 2015 Society of Plastics Engineers     

不同成核剂成核聚丙烯的结晶行为与力学性能

制备了６种成核剂成核聚丙烯（ＰＰ）母料研究了成核母料和成核母料／ＰＰ的结晶,熔融行为,力学性能和透明性等物理性能,不同成核在成核母材料和成核母料／ＰＰ中对ＰＰ的结晶与熔融行为以及性能有不同的作用,观察到成核型Ａ成核ＰＰ具有较高的结晶温度与综合性能,而成核剂Ｂ成核ＰＰ的透明性较好。     

Crystallization of polypropylene near the surface in injection‐molded plaques: A comparison of morphology and a numerical analysis

Skin morphology formation on injection‐molded isotactic polypropylene (PP) was investigated using micro‐beam synchrotron wide‐angle X‐ray diffraction and numerical simulation. The 1–20 μm depth range was characterized with an X‐ray beam of 0.273 μm χ 0.389 μm in size. From an evaluation of doping nucleating agents (NA) in PP, the NAs did not work at a depth of 1 μm. α‐specified NA affected crystallization within a 5‐μm depth. β‐specified PP showed α‐form crystallinity at the 5–20 μm depth. The mesomorphic crystal near the surface showed extremely high orientation. From viscoelastic flow simulation, PP molecules near the surface were oriented in the flow direction by extensional flow in the flow front, but freezing occurred faster than flow‐induced crystallization. It was estimated that the delay of crystallization occurred during the transient temperature. The deformation rate did not cause a difference in crystal morphology near the surface, but the cooling rate did. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

己二酸/无水硫酸钙晶须改性PP的等温结晶动力学

通过差示扫描量热(DSC)仪分析了己二酸(AA)和无水硫酸钙晶须(ACSW)复配改性聚丙烯(PP)的等温结晶行为,用偏光显微镜(PLM)观察了AA/ACSW复配改性PP的晶体形貌。DSC分析结果表明,随着结晶温度升高,半结晶时间和最大结晶时间增加,半结晶速率降低;与纯PP相比,ACSW和AA/ACSW复合改性都能使PP的结晶时间降低,结晶效率增加,说明ACSW和AA/ACSW对PP具有异相成核作用,并且AA/ACSW复合改性PP对提高PP的结晶性能有更好的效果,此外ACSW改性PP的等温结晶活化能最低。对改性PP的PLM的观察说明ACSW对PP具有异相成核作用,而AA/ACSW对PP的β晶成核具有协同促进作用。     

Effect of zeolite 5A on the crystalline behavior of polypropylene (PP) in PP/β‐nucleating agent system

The effect of zeolite 5A on the crystalline behavior of polypropylene (PP) in PP/β‐nucleating agent system was investigated with X‐ray diffractometer (XRD), differential scanning calorimeter (DSC), and polarized light microscope (PLM) in this study. Zeolite 5A has less effect on crystalline phase of PP/β‐nucleating agent than does n‐CaCO₃, which is ascribed to the stronger surficial polarity and better dispersibility of zeolite 5A. The data of DSC indicated that the crystallization peak temperature of PP increases by 8.3°C in the presence of zeolite 5A, and n‐CaCO₃ increases 5.7°C in PP/TMB‐5 system, relative to pure PP. And the initial crystallization temperature (T_c0) and the relative crystallinity (X_c) of PP is much more dramatically raised in the presence of zeolite 5A than CaCO₃. The efficiency of zeolite 5A in reducing the spherulites size of PP was seen clearly from the PLM photographs. The mechanical testing results showed that the flexural strength and impact strength of PP/β‐nucleating agent system increased in the presence of zeolite 5A. POLYM. COMPOS., 2008. © Society of Plastics Engineers     

Effect of syndiotactic polystyrene on the crystallization behavior of isotactic polypropylene/syndiotactic polystyrene blends with and without β‐nucleating agent

Blends of isotactic polypropylene (PP) and syndiotactic polystyrene (sPS) with and without β‐nucleating agent were prepared using a twin‐screw extruder at 290 °C. Blends of PP/sPS with β‐nucleating agent mainly show β crystalline form, irrespective of high (20 °C min^?1) or low (2 °C min^?1) previous cooling rates. This suggests that the cooling rates have little effect on the polymorphic composition of PP in PP/sPS blends. The effect of sPS on the crystallization of PP is compared with that of polyamide 6 (PA6). The increase in crystallization temperature of PP is smaller in the presence of sPS than in the presence of PA6; the fold surface free energy of PP/sPS is larger than that of PP/PA6 blends. These results reveal that compared with PA6, sPS has much weaker α‐nucleation effect on the crystallization of PP. The weak α‐nucleation effect of sPS is attributed to the high lattice mismatch between PP and sPS crystals.     

Effect of DMDBS (3 : 2, 4‐bis(3,4‐dimethyldibenzylidene) sorbitol) and NA11 (sodium 2,2′‐methylene‐bis(4,6‐di‐tertbutylphenyl)‐phosphate) on electret properties of polypropylene filaments

Polypropylene (PP) composite filaments containing two different nucleating agents—DMDBS (3 : 2, 4‐bis(3,4‐dimethyldibenzylidene) sorbitol) and NA11 (sodium 2,2′‐methylene‐bis(4,6‐di‐tertbutylphenyl)‐phosphate) were melt spun to modify polymer electrostatic charging characteristics. Sample filaments were charged with a corona instrument and their surface potentials were measured. Initial surface potential as well as potential stability was monitored through an accelerated decay procedure. NA11 was found to be more efficient as an electret additive leading to a 50% increase in charge stability. Filaments with DMDBS exhibited a faster decay. Charging at elevated temperatures resulted in enhanced charge density and stability for both additives. The fiber microstructure was examined by Wide Angle X‐ray Diffraction and Differential Scanning Calorimetry. Rather than reducing the crystal sizes, X‐Ray diffractograms suggest that the crystal size increases with the addition of nucleating agents, while the degree of crystallinity appears to remain unaltered. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2068–2075, 2013     

Crystallization behavior of carbon black‐filled polypropylene and polypropylene/epoxy composites

The crystallization behavior of polypropylene (PP)/carbon black (CB) and PP/epoxy/CB composites was studied with differential scanning calorimetry (DSC). The effects of compatibilizer MAH‐g‐PP and dynamic cure on the crystallization behavior are investigated. The nonisothermal crystallization parameters analysis showed that CB particles in the PP/CB composites and the dispersed epoxy particles in the PP/epoxy composites could act as nucleating agents, accelerating the crystallization of the composites. Morphological studies indicated that the incorporation of CB into PP/epoxy resulted in its preferential localization in the epoxy resin phase, changing the spherical epoxy particles into elongated structure, and thus reduced the nucleation effect of epoxy particles. Addition of MAH‐g‐PP significantly decreased the average diameter of epoxy particles in the PP/epoxy and PP/epoxy/CB composites, promoting the crystallization of PP more effectively. The isothermal crystallization kinetics and thermodynamics of the PP/CB and PP/epoxy/CB composites were studied with the Avrami equation and Hoffman theory, respectively. The Avrami exponent and the crystallization rate of the PP/CB composites were higher than those of PP, and the free energy of chain folding for PP crystallization decreased with increasing CB content. Addition of MAH‐g‐PP into the PP/epoxy and PP/epoxy/CB composites increased the crystallization rate of the composites and decreased the chain folding energy significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 104–118, 2006