Crystal phases,structure, and orientation in isotactic polypropylene after isothermal crystallization under oscillatory shear as a function of nucleation agent

2D wide-angle X-ray diffraction (2D-WAXD) measurement was performed to investigate the effects of both oscillatory shear and the nucleating agent on the crystalline structure distribution and orientation of isotactic polypropylene (iPP). 1,3:2,4-bis(p-methylbenzylidene) sorbitol (MDBS) and 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS) can induce α-PP and β-PP simultaneously. The presence of MDBS (or DMDBS) and oscillatory strain (oscillatory frequency is fixed) exhibits a synergistic interaction on increasing the content of β-crystals of iPP. Under the oscillatory shear field at the fixed oscillatory strain, the β-crystal content and the orientation of iPP with and without MDBS (or DMDBS) change slightly with the increase of the oscillatory frequency. Comparing with MDBS (or DMDBS) nucleated iPP crystallization under shear field, the periodically changed flow direction of the oscillatory shear field leads to the shorter α-row nuclei, weaker orientation but more β-crystals of the nucleated iPP.     

Crystallization studies of isotactic polypropylene containing nanostructured polyhedral oligomeric silsesquioxane molecules under quiescent and shear conditions

Crystallization studies at quiescent and shear states in isotactic polypropylene (iPP) containing nanostructured polyhedral oligomeric silsesquioxane (POSS) molecules were performed with in situ small‐angle X‐ray scattering (SAXS) and differential scanning calorimetry (DSC). DSC was used to characterize the quiescent crystallization behavior. It was observed that the addition of POSS molecules increased the crystallization rate of iPP under both isothermal and nonisothermal conditions, which suggests that POSS crystals act as nucleating agents. Furthermore, the crystallization rate was significantly reduced at a POSS concentration of 30 wt %, which suggests a retarded growth mechanism due to the molecular dispersion of POSS in the matrix. In situ SAXS was used to study the behavior of shear‐induced crystallization at temperatures of 140, 145, and 150 °C in samples with POSS concentrations of 10, 20, and 30 wt %. The SAXS patterns showed scattering maxima along the shear direction, which corresponded to a lamellar structure developed perpendicularly to the flow direction. The crystallization half‐time was calculated from the total scattered intensity of the SAXS image. The oriented fraction, defined as the fraction of scattered intensity from the oriented component to the total scattered intensity, was also calculated. The addition of POSS significantly increased the crystallization rate during shear compared with the rate for the neat polymer without POSS. We postulate that although POSS crystals have a limited role in shear‐induced crystallization, molecularly dispersed POSS molecules behave as weak crosslinkers in polymer melts and increase the relaxation time of iPP chains after shear. Therefore, the overall orientation of the polymer chains is improved and a faster crystallization rate is obtained with the addition of POSS. Moreover, higher POSS concentrations resulted in faster crystallization rates during shear. The addition of POSS decreased the average long‐period value of crystallized iPP after shear, which indicates that iPP nuclei are probably initiated in large numbers near molecularly dispersed POSS molecules. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2727–2739, 2001     

Crystallization behavior and morphological development of isotactic polypropylene blended with nanostructured polyhedral oligomeric silsesquioxane molecules

The thermal properties and morphological development of isothermally crystallized isotactic polypropylene (iPP) blended with nanostructured polyhedral oligomeric silsesquioxane (POSS) molecules at very small loading of POSS were studied with differential scanning calorimeter (DSC), thermal gravimetric analysis, dynamic mechanical analysis, polarized optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). The result of DSC indicated that the crystallization rate of iPP increases with the increase in POSS contents during crystallization; moreover, the melting temperature of iPP/POSS nanocomposites slightly decreases, while the heat of fusion increases with the addition of POSS molecules at melting and remelting traces. The storage modulus and thermal stability, respectively, remarkably decrease, while the glass transition temperature of isothermally crystallized iPP/POSS nanocomposites increases slightly with the increase in POSS contents. The morphologies results of WAXD and POM show that the POSS molecules form about 35 nm sized nanocrystals and aggregate to form thread‐like and network structure morphologies, respectively, in the molten state even when the POSS content is very small. These results, therefore, suggest that the interaction force between the POSS molecules should be larger than the force between POSS molecules and iPP matrix; however, those interactions depend on the chain length of functionalized substituents on the POSS cage. Therefore, the POSS molecules aggregate forming nanocrystals and act as an effective nucleating agent for iPP and influence the thermal properties of iPP/POSS nanocomposites due to the shorter chain length of functionalized substituents, methyl, on the POSS cage. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2122–2134, 2006     

The variable role of clay on the crystallization behavior of DMDBS-nucleated polypropylene

The effect of clay on the nucleating behavior of 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol(DMDBS) in cryatallization of isotactic polypropylene(iPP) was investigated by means of differential scanning calorimetry(DSC), dynamic rheology and polarized light microscopy(PLM).It is interesting to note that the incorporation of layered clay nanoparticles into DMDBS-nucleated iPP may induce a synergetic nucleation effect while the DMDBS content is below 0.1 wt%,otherwise it restricts the crystallization rate prominently as the DMDBS content increases up to 0.3 wt%,which has exceeded the content threshold to yield a nucleating agent(NA) network.As shown by dynamic rheological investigations, the clay nanoparticles demonstrate an obstructive effect of disturbing the consistency of DMDBS fibrils network.Moreover, to further demonstrate the importance of NA network formation in the crystallization of iPP,we used another NA named HPN-20e,which can not form network structure at all over the concentration studied,for comparison.In this case,the nucleated-crystallization rate is independent on the addition of clay nanoparticles,as the nucleating mechanism is an individual nuclei manner without NA network forming.     

Crystallization and melting behavior of isotactic polypropylene nucleated with individual and compound nucleating agents

In this study, α-phase nucleating agent (NA) 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (DMDBS), β-phase rare earth NA (WBG), and their compound NAs were introduced into isotactic polypropylene (iPP) matrix, respectively. Crystallization kinetics and subsequent melting behavior of the nucleated iPPs were comparatively studied by differential scanning calorimetry (DSC) under both isothermal and nonisothermal conditions. For the isothermal crystallization process, it is found that the Avrami model successfully described the crystallization kinetics. The active energy of nonisothermal crystallization of iPP was determined by the Kissinger method and showed that the addition of nucleating agents increased the activation energy. Melting behavior and crystalline structure of the nucleated iPPs are dependent on the nature of NAs and crystallization conditions. Higher proportion of β-phase can be obtained at higher content of β-nucleating agent and lower crystallization temperature or lower cooling rate.     

Crystallization behavior of sorbitol derivative nucleated polypropylene block copolymer under high pressure

The preparation of γ-phase in polypropylene is still an interesting issue in a long-term. In this work, we introduced a highly effective α-phase nucleating agent 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol derivatives (DMDBS) into polypropylene block copolymer (PPB) and investigated the crystallization behaviors of nucleated PPB sample under high pressure. The crystallization and melting behaviors of samples were characterized by differential scanning calorimetry, and the crystalline structure as well as the relative fraction of γ-phase in the sample was characterized by wide-angle X-ray diffraction (WAXD) and two-dimensional WAXD. Scanning electron microscope was used to characterize the supermolecular structure of samples. The results show that the effects of DMDBS and high pressure on crystallization behavior of PPB were dependent on the content of DMDBS. When the content of DMDBS is smaller than the critical value, there is a synergistic effect between DMDBS and high pressure to promote the formation of γ-phase. Specifically, the critical pressure under which γ-phase dominates completely is also decreased dramatically. When the content of DMDBS is higher than the critical value, there is a competition between the effect of DMDBS, which promotes the formation of α-phase and the effect of high pressure which promotes the formation of γ-phase.     

Mechanistic Insights into the Shear Effects on Isotactic Polypropylene Crystallization Containing β-Nucleating Agent

The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5(iPP/TMB-5) were investigated by synchrotron radiation wide angel X-ray diffraction(SR-WAXD), differential scanning calorimeter(DSC) and polarized light microscope(PLM). It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within mesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures.     

Study of the crystallization behaviors of isotactic polypropylene with sodium benzoate as a specific versatile nucleating agent

Sodium benzoate (SB), a conventional nucleating agent of α‐phase isotactic polypropylene (iPP) was discovered to induce the creation of β‐phase iPP under certain crystalline conditions. Polarized optical microscopy (POM) and wide angle X‐ray diffraction (WAXD) were carried out to verify the versatile nucleating activity of SB and investigate the influences of SB's content, isothermal crystallization temperature, and crystallization time on the formation of β‐phase iPP. The current experimental results indicated that, under isothermal crystallization conditions, SB showed peculiar nucleating characteristics on inducing iPP crystallization which were different from those of the commercial β form nucleating agent (TMB‐5). The content of β crystal form of iPP nucleated with SB (PP/SB) increased initially with the increase of crystallization temperature, nucleating agent (SB) percentage or crystallization time, reached a maximum value, and then decreased as the crystallization temperature, nucleating agent percentage or crystallization time further increased. While the content of β crystal form of iPP nucleated with TMB‐5 (PP/TMB‐5) showed a completely different changing pattern with the crystallization conditions. The obvious difference of the two kinds of nucleating agents on inducing iPP crystallization can be explained by the versatile nucleating ability of SB. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1183–1192, 2008     

等规聚丙烯在γ射线辐照下的链结构和结晶行为

利用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和示差扫描量热(DSC)等手段对不同剂量γ射线辐照后等规聚丙烯(iPP)的分子链结构及结晶行为的变化进行了研究.结果表明,γ射线辐照使iPP的分子量下降,并在其分子链中产生羟基和羰基等极性基团,从而影响其结晶行为.在非等温结晶过程中,当辐照剂量≤50 kGy时,iPP的热结晶温度略有升高;增大辐照剂量,iPP的热结晶温度明显降低.iPP的熔融温度则随辐照剂量的增大而降低,且分裂成双峰.利用Avrami方程研究了辐照前后iPP的等温结晶动力学,发现辐照前后样品的Avrami指数n都在3左右,表明iPP的结晶遵循异相成核机理,且不受辐照剂量和等温结晶温度的影响,但总结晶速率随等温结晶温度和辐照剂量的升高而逐渐减小.探讨了iPP经过γ射线辐照后,分子链断裂、链结构变化和结晶速率之间的关系.     

Effect of nucleating agent on the brittle–ductile transition behavior of polypropylene/ethylene–octene copolymer blends

In the present work, α‐form nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988) is introduced into the blends of polypropylene/ethylene–octene copolymer (PP/POE) blends to study the effect of the nucleating agent on the toughness of PP/POE blends through affecting the crystallization behavior of PP matrix. Compared with the PP/POE blends, in which the toughness of the blends increases gradually with the increasing content of POE and only a weak transition in toughness is observed, addition of 0.2 wt % DMDBS induces not only the definitely brittle‐ductile transition at low POE content but also the enhancement of toughness and tensile strength of the blends simultaneously. Study on the morphologies of impact‐fractured surfaces suggests that the addition of a few amounts of DMDBS increases the degree of plastic deformation of sample during the fracture process. WAXD results suggest that POE induces the formation of the β‐form crystalline of PP; however, DMDBS prevents the formation of it. SEM results show that the addition of DMDBS does not affect the dispersion and phase morphologies of POE particles in PP matrix. DSC and POM results show that, although POE acts as a nucleating agent for PP crystallization and which enhances the crystallization temperature of PP and decreases the spherulites size of PP slightly, DMDBS induces the enhancement of the crystallization temperature of PP and the decrease of spherulites size of PP more greatly. It is concluded that the definitely brittle–ductile transition behavior during the impact process and the great improvement of toughness of the blends are attributed to the sharp decrease of PP spherulites size and their homogeneous distribution obtained by the addition of nucleating agent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 577–588, 2008     

Nucleation effect of cyclodextrin inclusion compounds on the crystallization of polypropylene

The β‐cyclodextrin (β‐CD) and γ‐cyclodextrin (γ‐CD) inclusion compounds (ICs) with two different molecular weight isotactic polypropylene (iPP) were prepared. The ICs with high molecular weight iPP as guest molecule had lower inclusion rate. The crystallization behavior of iPP blended with the CDs and ICs was investigated by differential scanning calorimetry, polarized optical microscopy, and light scattering. The iPP blended with the ICs was found to exhibit higher crystallization temperature (T_C), smaller spherulites, and faster crystallization rate than those of neat iPP. These results indicate that the ICs play a role of nucleating agent on the crystallization of iPP and induce the accelerated crystallization. Both β‐CD‐iPP ICs and γ‐CD‐iPP ICs with longer iPP molecular chains had better nucleation effect than the ICs with shorter iPP molecular chains. This suggested that the nucleation effect of these ICs was affected by the inclusion rate of ICs. The lower inclusion rate could result in better nucleation effect, due to the interaction of extended iPP molecules inside the CD cavity and iPP molecules in the matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 130–137, 2009     

Isothermal crystallization kinetics of polypropylene/POSS composites

Polypropylene (PP)/octavinyl polyhedral oligomeric silsesquioxane (POSS) composites were prepared by two different processing methods: reactive blending and physical blending, and the crystallization behavior of PP and PP/POSS composites was studied by means of differential scanning calorimetry and polarized optical microscope. The results showed that the crystallization of PP in PP/POSS composites was strongly influenced by the different processing methods. POSS particles can act as effective nucleating agent, accelerating the crystallization of PP. The crystallization rate increased more dramatically for the reactive blending composite due to the stronger nucleating effect of PP grafted POSS. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1762–1772, 2008     

Effects of microparticles on isotactic polypropylene: Thermomechanical and thermal properties

Five types of melamine-formaldehyde microcapsules, that is, with shells of different compositions [melamine formaldehyde shell or a melamine formaldehyde-poly(hexamethylene adipate glycol) shell] and containing or not a flame retardant, diammonium hydrogen phosphate (DAHP), have been prepared by an in situ polymerization method and have been added to an isotactic polypropylene matrix (iPP) by melt blending at 5 wt %. Wide-angle X-ray diffraction and differential scanning calorimetry were employed to investigate the crystallization behavior of the prepared iPP/microparticles composites. The tensile properties and the thermal stability were also evaluated. It was stated that the morphology and the shape of the microparticles not only influence the crystallization behavior but also the thermomechanical properties of these composites. Thus, rougher microparticles act as a nucleating agent for the iPP, and in the presence of microparticles containing DAHP, the α- and the β-crystals are formed. Moreover, the presence of microparticles improves the thermal stability of the iPP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2566–2576, 2008     

等规聚丙烯自成核的等温结晶动力学

近年来 ,有关等规聚丙烯 (i PP)的自成核研究已引起了人们的关注 [1 ] ,但有关其结晶动力学的报道并不多见 .Carfagna等 [2 ]用膨胀计法研究了 i PP在未完全熔融重结晶情况下的等温结晶动力学 ,得到的 Avrami指数远远小于 3 .张新远等[3 ] 研究了 i PP未完全熔融情况下的非等温结晶动力学 .到目前为止 ,i PP自成核的熔体降温等温结晶动力学尚未见报道 .本文在 i PP自成核研究的基础上 [4] ,用 DSC方法研究了 i PP自成核在较高温度下的等温结晶动力学 ,讨论了结晶机理 .结果表明 ,在本实验的自成核条件下 ,i PP依然是三维球晶生长 ,…     

Crystallization, mechanical and thermal properties of sorbitol derivatives nucleated polypropylene/calcium carbonate composites

<正>The effect ofαphase nucleating agent(NA) 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol(DMDBS) on crystallization and physical properties of polypropylene/calcium carbonate(PP/CaCO_3) composites has been comparatively investigated.Compared with binary PP/CaCO_3 composites,in which CaCO_3 exhibits weak heterogeneous nucleation, inconspicuous reinforcement and toughening effects for PP,the introduction of a few amounts of DMDBS induces a great increase of the degree of crystallinity.Largely improved tensile properties,fracture toughness at relatively higher temperature and heat deformation temperature(HDT) are observed for DMDBS nucleated PP/CaCO_3 composites.     

Crystallization kinetics of isotactic polypropylene nucleated with octamethylenedicarboxylic dibenzoylhydrazide under isothermal and non-isothermal conditions

Octamethylenedicarboxylic dibenzoylhydrazide (TMC-300) was used as a nucleating agent for isotactic polypropylene (iPP) for the first time. The Avrami method and the Caze method were used to analyze the isothermal and non-isothermal crystallization kinetics of iPP incorporated with TMC-300, respectively. During isothermal crystallization, the half crystallization time at 130 °C reduces from 130 s of virgin iPP to 44 s after addition of TMC-300, which reflects that TMC-300 increased the crystallization rate of iPP obviously. The crystallization activation energy decreases from 382.5 kJ mol^?1 of virgin iPP to 275.3 kJ mol^?1 of iPP/TMC-300. During non-isothermal crystallization, the crystallization peak temperature of iPP nucleated with TMC-300 was increased by 5.1 °C when compared to that of virgin iPP at the cooling rate of 20 °C min^?1, and both the reduction of half crystallization time and the increase in peak crystallization temperature also justified that the addition of TMC-300 accelerated the crystallization of iPP.

     

Non-isothermal crystallization behavior of polypropylene with nucleating agents and nano-calcium carbonate

The non-isothermal crystallization kinetics of isotactic polypropylene (iPP) and nucleated iPP was investigated by DSC. The crystalline morphology of iPP was observed by polarized light microscopy. It was found that the crystallization rate increased with the addition of nanometer-scale calcium carbonate (nm-CaCO₃) particles. The addition of dibenzylidene sorbitol (DBS) could greatly reduce the spherulite size of iPP. The crystallization temperature for the iPP with DBS was higher than for non-nucleated iPP. DBS was an effective nucleating agent for iPP. The results of measurements suggested that there was a coordinated action to the crystallization of iPP when the organic nucleating agents (DBS) and nm-CaCO₃ were added to iPP together. Comparison to the modified Avrami equation and Ozawa equation, another method—Mo’s method can describe the non-isothermal crystallization behavior of iPP and nucleated iPP more satisfactorily.     

Effects of nucleating agent 1,3,5-benzenetricarboxylic acid tris(cyclohexylamide) on properties and crystallization behaviors of isotactic polypropylene

Amide derivatives of 1,3,5-benzenetricarboxylic acid are a type of novel nucleating agents for isotactic polypropylene (iPP). Effects of nucleating agent 1,3,5-benzenetricarboxylic acid tris(cyclohexylamide) (BTCA-TCHA) on properties and crystallization behaviors of iPP were investigated and the results were compared with those of iPP nucleated with a highly effective commercial nucleating agent Millad 3988. The results showed that BTCA-TCHA was highly effective and it improved greatly the mechanical and optical properties of iPP and increased crystallization peak temperature of iPP obviously. When the addition concentration of BTCA-TCHA was 0.2 wt.%, tensile strength and flexural modulus of iPP were increased by 9.7 and 12.4 %, respectively, and the haze value of iPP was decreased by 53.5 %. When the cooling rate was 20 °C/min, the crystallization peak temperature of iPP was increased from 114.6 °C of virgin iPP to 126.8 °C. In addition, it was found that the nucleation efficiency of BTCA-TCHA was comparable for that of Millad 3988.     

Effect of Clay/Diamond and Clay/Carbon Nanosystems on Structure-Properties Relationships of iPP

The effect of the addition of two combined fillers, smectite clay and diamond and smectite clay and carbon nanoparticles, on structure, morphology, isothermal and non isothermal crystallization behaviour, tensile and thermal properties of isotactic polypropylene (iPP) has been investigated by using several techniques: wide angle X-ray diffraction, optical and scanning electron microscopy, thermogravimetry, differential scanning calorimetry and tensile techniques. It was found that nanoparticles of diamond and carbon favour the nucleation of the β-form of iPP crystal, whereas the clay nanolayers do not have any influence on the crystal structure of iPP. The thermal stability of iPP/(clay+diamond) and iPP/(clay+carbon) is improved with respect to neat iPP, whereas no influence is detected when only clay is added to iPP. At the given crystallization conditions, the overall crystallization peak of iPP/(clay+diamond) almost exactly overlaps the crystallization peak of neat iPP, whereas in the case of iPP/clay and iPP/(clay+carbon) the maximum of the crystallization peaks is shifted to higher temperature. The spherulite growth rate, G values do not differ from one another. The iPP/(clay+carbon) system shows ductile behavior. The other systems show brittle behavior with failure before necking. These results were related with the very high percentage of beta phase present in the samples of iPP/(clay+carbon).     

Non-isothermal crystallization kinetics of β-nucleated isotactic polypropylene

Isotactic polypropylenes (iPP) samples were incorporated with two β-nucleating agents (NT-A and NT-C), respectively, and their non-isothermal crystallization and subsequent melt behaviors were investigated by means of differential scanning calorimeter. Jeziorny, Ozawa, and Mo methods were used to analyze non-isothermal crystallization kinetics of pure iPP and β-nucleated iPP samples. The activation energies (ΔE) of non-isothermal crystallization were calculated by Kissinger method. And the nucleation activities were calculated according to the Dobreva method. It is found that the crystallization temperature decreases and the crystallization rate increases with increasing cooling rate. The crystallization temperature and crystallization rate of nucleated iPP are higher than those of pure iPP. The order of ΔE is NT-A/iPP > pure iPP > NT-C/iPP. NT-C is more efficient than NT-A as a β-nucleating agent. But the non-isothermal crystallization kinetics of α- and β-phases cannot be determined separately. The present results should be considered with caution.