Multiple melting behavior of isotactic polypropylene and poly(propylene-co-ethylene) after stepwise isothermal crystallization

The multiple melting behavior of several commercial resins of isotactic polypropylene (iPP) and random copolymer, poly(propylene-co-ethylene) (PPE), after stepwise isothermal crystallization (SIC) were studied by differential scanning calorimeter and wide-angle X-ray diffraction (WAXD). For iPP samples, three typical melting endotherms appeared after SIC process when heating rate was lower than 10 °C/min. The WAXD experiments proved that only α-form crystal was formed during SIC process and no transition from α1- to α2-form occurred during heating process. Heating rate dependence for each endotherm was discussed and it was concluded that there were only two major crystals with different thermal stability. For the PPE sample, more melting endotherms appeared after stepwise isothermal crystallization. The introduction of ethylene comonomer in isotactic propylene backbone further decreased the regularity of molecular chain, and the short isotactic propylene sequences could crystallize into γ-form crystal having a low melting temperature whereas the long sequences crystallized into α-form crystal having high melting temperature.     

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 ,…     

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 the γ‐form crystal on the thermal fractionation of poly(propylene‐co‐ethylene)

The effect of the γ‐form crystal on the thermal fractionation of a commercial poly(propylene‐co‐ethylene) (PPE) has been studied by differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) techniques. Two thermal fractionation techniques, stepwise isothermal crystallization (SIC) and successive self‐nucleation and annealing (SSA), have been used to characterize the molecular heterogeneity of the PPE. The results indicate that the SSA technique possesses a stronger fractionation ability than that of the SIC technique. The heating scan of the SSA fractionated sample exhibits 12 endothermic peaks, whereas the scan of the SIC fractionated sample only shows eight melting peaks. The WAXD observations of the fractionated PPE samples prove that the content of the γ‐form crystals formed during the thermal treatment of the SIC technique is much higher than that of the SSA treatment. The former is 57.4%, whereas the later is 12.6%. The effect of theγ‐form crystals on thermal fractionation ability is discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4320–4325, 2004     

Polymerization control and fast characterization of the stereo-defect distribution of heterogeneous Ziegler–Natta isotactic polypropylene

Adjustment of the stereo-defects distribution of isotactic polypropylene (iPP) is important for obtaining better properties of the resins in Ziegler–Natta polymerization. In this study, in order to adjust the stereo-defect distribution of iPP prepared by the Spheripol process (Basell), the cocatalyst/external donor (triethylaluminium/dicyclopentyldimethoxysilane, Al/Si) mole ratio was gradually changed from 30 to 36, accompanied with hydrogen adjustment. And we obtained a series of iPP samples (A–E). The characterization of ¹³C NMR, xylene soluble fraction (XS) showed the average isotacticity of the obtained samples are nearly same, but the results of high resolution ¹³C NMR, temperature rising elution fractionation (TREF) and xylene solvent fractionation indicated that, as the Al/Si ratio increases, the amount of high isotacticity in iPP gradually decreases, the amount of medium and low isotacticity gradually increased, the distribution of stereo-defects becomes more uniform.A relative time-saving method, successive self-nucleation and annealing (SSA) fractionation was applied to evaluate the stereo-defect distribution of iPP. A calibration which can be used to convert SSA final melting curves to the average meso sequence length curves was constructed. A good agreement between ¹³C NMR, XS, TREF results and SSA fractionation results indicated that it is feasible by using SSA to provide quick characterize of the stereo-defect distribution of iPP.     

Thermodynamics of Micellization from Heat‐Capacity Measurements

Differential scanning calorimetry (DSC), the most important technique for studying the thermodynamics of structural transitions of biological macromolecules, is seldom used in quantitative thermodynamic studies of surfactant micellization/demicellization. The reason for this could be ascribed to an insufficient understanding of the temperature dependence of the heat capacity of surfactant solutions (DSC data) in terms of thermodynamics, which leads to problems with the design of experiments and interpretation of the output signals. We address these issues by careful design of DSC experiments performed with solutions of ionic and nonionic surfactants at various surfactant concentrations, and individual and global mass‐action model analysis of the obtained DSC data. Our approach leads to reliable thermodynamic parameters of micellization for all types of surfactants, comparable with those obtained by using isothermal titration calorimetry (ITC). In summary, we demonstrate that DSC can be successfully used as an independent method to obtain temperature‐dependent thermodynamic parameters for micellization.     

Isotactic polypropylene reversible crystallization investigated by modulated temperature and quasi‐isothermal FTIR

Modulated temperature techniques allow to separate the reversing and non‐reversing contributions of material transitions. To investigate reversible crystallization and melting of isotactic polypropylene (iPP) at microstructural level, in this research, modulated temperature Fourier transform infrared (MTFTIR) and quasi‐isothermal FTIR (QIFTIR) analyses are used. By following the intensity variation of iPP regularity bands, associated with 3₁ helix structures of different lengths (n repeating units), MTFTIR evidences that, independently from helix length, a reversing coil–helix transition takes place few degrees below the non‐reversing crystallization onset. By comparing spectroscopic and differential scanning calorimetry experiments performed in quasi‐isothermal conditions, the reversing transition was found to be associated with the reversible melting‐crystallization phenomenon. Moreover, QIFTIR evidences that helices of different lengths contribute differently to the reversible transition: the helices composed of n = 10 and n = 12 are active into all the explored temperature range (30–130 °C) whereas the shortest (n = 6) and the longest (n > 15) helices contribute to reversibility at T > 100 °C. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 922–931     

Influence of specimen thickness on isothermal crystallization kinetics. A theoretical analysis

In the DSC technique, isothermal crystallization experiments are usually performed on thin flat specimens, but their interpretation generally uses theories developed for an unbounded volume. In this paper, isothermal crystallization of spherical entities in the volume limited by two parallel infinite planes is considered. Our model, derived from Avrami's theory, gives an analytical expression for the transformed volume fraction as a function of time. It is shown that the influence of thickness becomes important when thickness becomes of the order of or smaller than the average spherulite radius. The main effects of a decreasing thickness are a slower crystallization kinetics and a decrease in the Avrami exponent. These results can be used to interpret experimental data obtained in isothermal polymer crystallization.     

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     

等规聚丙烯/二元乙丙橡胶合金相分离对结晶动力学的影响

用小角激光光散射(SALLS)、相差显微镜(PCM)、示差扫描量热仪(DSC)和偏光显微镜(POM)研究了聚丙烯/二元乙丙橡胶(iPP/EPR)共混体系的相分离行为和等温结晶行为.发现iPP/EPR(50/50,W/W)发生的液-液相分离遵循spinodal机理.通过Cahn-Hilliard方程求得了不同实验温度下iPP/EPR的表观扩散系数(Dapp)以及spinodal温度(Ts).考察了不同相分离程度的iPP/EPR体系结晶动力学,发现延长相分离时间(tps)或提高相分离温度(Tps)均会导致半结晶时间(t1/2)增大,即结晶速率降低.这被归于EPR成核作用的降低.动力学分析结果表明Avrami模型适用于描述该体系的等温结晶过程,其结晶机理基本不受相分离程度的影响,结晶均以瞬时成核和三维生长为主.     

Isothermal crystallization behaviors of isotactic polypropylene nucleated with α/β compounding nucleating agents

Sodium 2,2′‐methylene‐bis(4,6‐di‐tert‐butylphenyl) phosphate (NA40) and N,N‐dicyclohexylterephthalamide (NABW) are high effective nucleating agents for inducing the formation of α‐isotactic polypropylene (α‐iPP) and β‐iPP, respectively. The isothermal crystallization kinetics of iPP nucleated with nucleating agents NABW, NA40/NABW (weight ratio of NA40 to NABW is 1:1) and NA40 were investigated by differential scanning calorimetry (DSC) and Avrami equation was adopted to analyze the experimental data. The results show that the addition of NABW, NA40/NABW and NA40 can shorten crystallization half‐time (t_1/2) and increase crystallization rate of iPP greatly. In these three nucleating agents, the α nucleating agent NA40 can shorten t_1/2 of iPP by the largest extent, which indicates that it has the best nucleation effect. While iPP nucleated with NA40/NABW compounding nucleating agents has shorter t_1/2 than iPP nucleated with NABW. The Avrami exponents of iPP and nucleated iPP are close to 3.0, which indicates that the addition of nucleating agents doesn't change the crystallization growth patterns of iPP under isothermal conditions and the crystal growth is heterogeneous three‐dimensional spherulitic growth. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 590–596, 2007     

Prediction of non-isothermal crystallization parameters for isotactic polypropylene

Non-isothermal crystallization kinetics of isotactic polypropylene (iPP) was simulated with the assumption that the non-isothermal crystallization process was composed of some finite isothermal crystallization processes, while each isothermal crystallization process consists of three main steps—induction, nucleation and crystal growth. In the simulation, induction time was taken into account, allowing one to make predictions on the start of the non-isothermal crystallization of iPP; nuclei density was treated as a function of temperature; the Hoffman–Lauritzen theory was employed to describe the spherulite growth rate varied with temperature, and the relative crystallinity was determined by the equation of Kolmogorov. Finally, model prediction was verified by quantitative comparison between the theoretical results with the experimental results.     

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     

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.     

Morphology and nonisothermal crystallization of in situ microfibrillar poly(ethylene terephthalate)/polypropylene blend fabricated through slit‐extrusion,hot‐stretch quenching

This study describes the morphology and nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) in situ micro‐fiber‐reinforced blends (MRB) obtained via slit‐extrusion, hot‐stretching quenching. For comparison purposes, neat PP and PET/PP common blends are also included. Morphological observation indicated that the well‐defined microfibers are in situ generated by the slit‐extrusion, hot‐stretching quenching process. Neat iPP and PET/iPP common blends showed the normal spherulite morphology, whereas the PET/iPP microfibrillar blend had typical transcrystallites at 1 wt % PET concentration. The nonisothermal crystallization kinetics of three samples were investigated with differential scanning calorimetry (DSC). Applying the theories proposed by Jeziorny, Ozawa, and Liu to analyze the crystallization kinetics of neat PP and PET/PP common and microfibrillar blends, agreement was found between our experimental results and Liu's prediction. The increases of crystallization temperature and crystallization rate during the nonisothermal crystallization process indicated that PET in situ microfibers have significant nucleation ability for the crystallization of a PP matrix phase. The crystallization peaks in the DSC curves of the three materials examined widened and shifted to lower temperature when the cooling rate was increased. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 374–385, 2004     

镧配合物对等规聚丙烯等温结晶性能的影响

利用Avrami方程和Lauritzen-Hoffman结晶动力学理论研究了一种镧配合物LaC对等规聚丙烯(iPP) 等温结晶行为的影响. 差示扫描量热法(DSC)和X射线衍射技术(XRD)研究表明, LaC的加入并未改变iPP的结晶形态, 但LaC的存在能提高体系的结晶度并显著加速iPP的结晶过程. 在130 ℃进行等温结晶时, 含0.5%LaC(质量分数)的iPP与纯iPP相比, Avrami指数n值无显著差异, 但前者总的结晶速率常数k值比后者提高约4倍,而半结晶时间t1/2值减少到后者的62%, Avrami方程分析结果表明LaC的存在主要起到增加晶核的作用. 利用Lauritzen-Hoffman结晶动力学理论, 通过对iPP在121 ℃、124 ℃、127 ℃和130 ℃下等温结晶的数据进行分析可知, 加入0.5%的LaC后, 体系的成核常数kg从纯PP的3.3×105 K2增加到PP/LaC的3.8×105 K2, 而结晶生长时大分子在垂直于分子链方向折叠的界面自由能σe从纯PP的0.223 J·m-2降低到PP/LaC的0.154 J·m-2, 表明LaC在iPP结晶过程中不仅起到增加晶核的作用, 同时使大分子链更易排入晶格, 即起到促进结晶成长的作用.     

Thermal behavior of isotactic polypropylene freeze-extracted from solutions with varying concentrations

Isotactic polypropylene (iPP) with narrow molecular mass distribution was freeze-extracted from n-octane solutions with varying concentrations. The recovered samples were characterized by differential scanning calorimetry. It is found that the sample recovered from the very dilute solution exhibits the higher non-isothermal crystallization temperature, faster isothermal crystallization rate, and smaller Avrami index. And there should exist a critical concentration corresponding with the critical overlap concentration proposed by de Gennes in the polymer solutions. In the solution well below the critical concentration, the iPP chains were isolated from each other, resulting in an acceleration of melt crystallization for the recovered samples. It seems that the chain entanglement is a barrier to the melt crystallization of polymer.     

Partial melting and recrystallization of isotactic polypropylene

<正>A relatively high predetermined crystallization temperature(135℃) was chosen to grow well developed iPP spherulites,then the partial melting was carried out at a temperature of 165℃,where the preformed spherulites were seen to only decrease their size but not completely melted.The crystallization behavior of partially melted isotactic polypropylene (iPP) has been carefully examined by different scanning calorimetry(DSC) and polarized light microscopy(PLM).The experimental results show that at a special annealing temperature(165℃) the melting behavior of iPP includes two parts with different mechanism,one part is the melting of iPP spherulite outside,another is the partial lamellae perfection during longer annealing time in the unmelted spherulite.The conformational orders of the iPP melt decrease with the increase of the annealing temperature.     

Crystallinity changes in plastically deformed isotactic polypropylene evaluated by x‐ray diffraction and differential scanning calorimetry methods

The crystallinity of isotactic polypropylene (iPP), when deformed with plastic plane‐strain compression, was studied with wide‐angle X‐ray scattering (WAXS) and differential scanning calorimetry (DSC) techniques. A comparison of the obtained crystallinity data with annealed iPP samples was performed. The material used in this study was commercial iPP (weight‐average molecular weight = 117.400 g/mol; number‐average molecular weight = 17.300 g/mol). A significant decrease in the crystallinity was observed with increasing deformation pressure when the X‐ray method was employed, whereas only a small decrease was registered when the DSC method of crystallinity determination was used. However, the annealed iPP samples demonstrated a slight crystallinity increase when evaluated by both techniques. The reason for the difference between WAXS and DSC crystallinity results is discussed. This study of iPP specimens subjected to large deformation led us to the conclusion that the WAXS method provides accurate crystallinity values for the deformed material, whereas the values obtained by the DSC method do not reproduce the real crystallinity of the deformed material. This is due to the inherent heating process of the method, which causes a relaxation process and a significant change in the crystallinity of the deformed material, providing values nearer to its intrinsic equilibrium state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 896–903, 2002     

Carbon nanoparticles as effective nucleating agents for polypropylene

The effect of four nucleating agents on the crystallization of isotactic polypropylene (iPP) was studied by differential scanning calorimetry (DSC) under isothermal and non-isothermal conditions. The nucleating agents are: carbon nanofibers (CNF), carbon nanotubes (CNT), lithium benzoate and dimethyl-benzylidene sorbitol. Avrami?s model is used to analyze the isothermal crystallization kinetics of iPP. Based on the increase in crystallization temperature (T _c) and the decrease in half-life time (τ_½) for crystallization, the most efficient nucleating agents are the CNF and CNT, at concentrations as low as 0.001 mass%. Sorbitol and lithium benzoate show to be less efficient, while the sorbitol needs to be present at concentrations above 0.05 mass% to even act as nucleating agent.