Effect of melt history on polymer crystallization

As discussed in this paper, melt treatment prior to crystallization, apparently proceeds by the following stages: partial melting; an insensitive region; and at higher temperatures, deactivation of nucleation sites. The deactivation-region onset temperature is quite dependent on the subsequent crystallization conditions and may not be observed in some polymers during crystallization from the melt. In addition, those polymers capable of being quenched directly from the melt to a non-crystalline glassy state and subsequently crystallized by reheating to above the glass transition, do not exhibit any more than a partial melting type melt treatment effect. The deactivation regime absence is a result of the homogeneous nucleation that occurs during crystallization from the quenched glassy state at temperatures slightly above the glass transition. Use of a metal- or glass-constraining medium does mask (at least partially) the effect of melt history upon crystallization from the melt. In addition to the masking effect of a constraining medium, some of the controversy in the literature pertaining to the existence of a melt treatment phenomenon may arise due to degredation of some polymers prior to the onset of the deactivation regime. The crystallization conditions employed are also quite influential on the possible effect melt treatment can have since the melt history phenomenon is noted by its effect on subsequent crystallization.     

The influence of structure and processing conditions on engineering mechanical properties in bulk crystallized isotactic polypropylene

A study of the influence of processing conditions and structure on engineering mechanical properties was conducted in bulk isotactic polypropylene. The influence of one processing parameter, undercooling, defined so as to account for both pressure and temperature effects, was particularly studied. Improved mechanical properties were found with increased undercooling. At low undercoolings, brittle failure without yield occurred, presumably the result of a sparsity of intercrystalline links under these conditions. As undercooling was increased, failure occurred after yielding as failure stress elevated dramatically, apparently because of greater link density. A modest improvement in yield stress with increased undercooling was attributed to the increasingly crosshatched lamellar structure produced at higher undercoolings, a structural trend confirmed by electron microscopy. Spherulite size, varied by altering melt history (melt temperature and time at melt temperature) at constant undercooling, was found to have no effect on engineering yield stress. This result indicates that apparent yield stress–spherulite size effects found by several earlier investigators were probably caused by structural variations other than spherulite size.     

Crystallization of linear polyethylene from melt in isothermal compression

Crystallization and primary nucleation of linear polyethylene has been studied by means of a custom-made miniature pressure apparatus. It has been shown that during isothermal compression of linear polyethylene melt at a constant rate crystallization occurs. In the range of fastest conversion rates the crystallization assumes isobaric character. The level of pressure at which the crystallization occurs increases with the increase of the crystal-lization temperature and/or with the increase of the compression rate. The crystallization has a spherulitic character up to the highest pressure achieved in the apparatus (approx. 600 MPa). Surprisingly, there are no dependencies of average spherulite size, degree of crystallinity, and lamellae thickness on the pressure and the temperature of crystallization during melt compression, but there is a strong relation to the compression rate. Below 250 MPa and above 300 MPa the crystallization proceeds under pressure, ensuring a constant undercooling. The undercooling for the pressure above 300 MPa is approximately 10°C lower than that for the pressure below 250 MPa. For the pressure 250–300 MPa a change in a primary nucleation and spherulite crystallization has been observed that is connected with the transformation from orthorhombic to pseudohexagonal symmetry of crystals. No noticeable effect of molecular weight of linear polyethylene on crystallization during iso-thermal melt compression has been observed.     

Effect of surface nucleation on isothermal crystallization kinetics: Theory, simulation and experiment

Surface nucleation of poly(l/d-lactide) at the interface with aluminum was studied by performing isothermal DSC analysis of amorphous samples of varying thickness between 100 °C and 130 °C. To ensure complete wetting of the aluminum surface, a hot melt laminating process was used to prepare the samples. Theoretical aspects of surface crystallization kinetics were explored and the resulting model was compared with the results of Monte-Carlo simulations. Three stages of surface crystallization were identified depending on the growth geometry: (1) impingement-free growth, (2) increasingly laterally-constrained transverse growth, and (3) interstitial growth. By fitting the Monte-Carlo simulation to the experimental half-times of crystallization the surface nucleation concentration and the bulk nucleation rate was estimated at 4 different temperatures. It was found that both surface nucleation concentration and the bulk nucleation concentration decrease with increasing crystallization temperature.     

Preparation and Assessment of Phase Morphology,Rheological Properties,and Thermal Behavior of Low-Density Polyethylene/Polyhexene-1 Blends

In this work, polyhexene-1 (PH-1) is synthesized by polymerization of hexane-1 with Ziegler–Natta catalyst and melt blended with low-density polyethylene (LDPE). The phase morphology, rheology, crystallization, and thermal behavior of (LDPE)/PH-1 blends are investigated. A good compatibility is observed in the blends up to 10?wt% PH-1 and the most of the droplets in the fractured surface are covered with and buried in the LDPE matrix and at higher percentage the droplet particle size significantly increased. The effect of microstructure of the blends on the flow behavior is studied by small amplitude oscillation rheology. By decreasing the compatibility and increasing the particle size, the Cole–Cole plots are deviated from the semi-circular shape at higher percentages than 10?wt% of PH-1. The change in the crystallization and melting behavior of LDPE in the blends are studied by differential scanning calorimetry and X-ray diffraction (XRD). It is found that by increasing the PH-1 the melting temperature of LDPE decreased from 112.5 to 110.8°C and crystallization temperature increased from 95.2 to 97.7°C which is evident of the nucleation effect. The intensity of (110) peak in XRD test declined as a remake of amorphous part of LDPE and the degree of crystallinity of LDPE decreased from 28 to 22% at 20?wt% PH-1.     

酒糟增强聚丙烯复合材料的制备与性能研究

通过熔融共混制备了酒糟(DG)增强聚丙烯(PP)复合材料,考察了DG用量、粒径以及马来酸酐接枝聚丙烯（PP-g-MAH）相容剂对复合材料性能的影响。结果表明,DG的加入使得复合材料的热稳定性和阻燃性能提高;PP/DG复合材料的结晶温度随DG含量的增加而升高,说明DG对PP有异相成核的作用;当粒径为100 μm 的DG用量为10 %（质量分数,下同）时,复合材料的缺口冲击强度相比纯PP提高了55.2 %;一定的粒径范围内,复合材料的力学性能与DG粒径呈正相关;PP-g-MAH含量为2 %,DG含量为10 %的复合材料的拉伸强度比未加相容剂时提高了9.3 %,比纯PP提高了4.1 %;PP-g-MAH的加入使得DG颗粒与PP基体间的界面结合明显改善。     

Crystallization behavior of poly(lactic acid)/elastomer blends

Differential Scanning Calorimetry (DSC) was used to evaluate the crystallization behavior of poly(lactic acid) and its blends with elastomer. It has been observed that the cold crystallization temperature of the blends decreased as the weight fraction of elastomer increased as well as the onset temperature of cold crystallization also shifted to lower temperature. In non-isothermal crystallization experiments, the crystallinity of poly(lactic acid) increased with a decrease in the heating and cooling rate. The melt crystallization of poly(lactic acid) appeared in the low cooling rate (1, 5 and 7.5 °C/min). The presence of low elastomer tends also to increase the crystallinity of poly (lactic acid). The DSC thermogram at ramp of 10 °C/min showed the maximum crystallinity of poly(lactic acid) is 36.95% with 20 wt% elastomer contents in blends. In isothermal crystallization, the cold crystallization rate increased with increasing crystallization temperature in the blends. The Avrami analysis showed that the cold crystallization was in two stages process and it was clearly seen at low temperature. The Avrami exponent (n) at first stage was varying from 1.59 to 2 which described a one-dimensional crystallization growth with homogeneous nucleation, whereas at second stage was varying from 2.09 to 2.71 which described the transitional mechanism to three dimensional crystallization growth with heterogeneous nucleation mechanism. The equilibrium melting point of poly(lactic acid) was also evaluated at 176 °C.     

Rapid crystallization of poly(l-lactic acid) induced by a nanoscaled zinc citrate complex as nucleating agent

A nanoscaled zinc citrate complex (ZnCC) was synthesized by the reaction of zinc acetate and citric acid using solution method. As a new eco-friendly nucleating agent, ZnCC was introduced into poly(l-lactic acid) (PLLA) via melt blending. The nonisothermal and isothermal crystallization, melting behavior, crystalline morphology and mechanical properties of the PLLA/ZnCC blends were investigated. It is found that ZnCC exhibits much more prominent nucleation activity on the crystallization of PLLA than conventional nucleating agent talc and commercial zinc citrate (ZnCit). By loading 0.05 wt% ZnCC, PLLA can complete crystallization upon cooling at 10 °C/min, and the crystallization peak shifts to a higher temperature with increasing ZnCC content. In the case of isothermal crystallization from the melt, the addition of ZnCC leads to a shorter crystallization time and a faster overall crystallization rate. Besides, the nucleation density of PLLA increases and the spherulite size decreases significantly in the presence of ZnCC. Epitaxy is the possible mechanism to elucidate the nucleation phenomenon of PLLA/ZnCC system. The tensile results show that ZnCC has a plasticization effect on the amorphous PLLA. Through a short-time annealing procedure, the mechanical properties such as tensile modulus and storage modulus of PLLA are improved by the addition of ZnCC.     

Effect of the nucleation mechanism on complex poly(L‐lactide) nonisothermal crystallization process. Part 1: Thermal and structural characterization

The effect of the holding temperature and time in the melt state of poly(L ‐lactide) (PLLA) samples on the nonisothermal melt crystallization process and on the structure have been investigated by means of DSC, polarized optical microscopy and wide angle X‐ray scattering. As standard starting material, single crystals grown from dilute solution were used. In the mild melting condition, the survived athermal nuclei favor high temperature polymer crystallization, while the more severe treatment leads the PLLA to crystallize at higher supercooling with a sporadic nucleation. At the intermediate melting temperature a distinct double nucleation mechanism was observed while at the lower nuclei concentration, a double crystallization rate was also found. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The influence of nucleation density and cooling rate on crystallization of polyethylene from the melt

Different samples of high-density polyethylene provided different nucleation densities which were assessed by optical microscopy and light scattering. Crystallizations were carried out under controlled cooling rates using a microscope hot stage and DSC from which crystallization temperatures were obtained. It is shown that the effective crystallization temperature is a function of the nucleation density, and a quantitative fit is found with theoretical predictions based on crystallization kinetics. The melting point was, in turn, found to be dependent on nucleation density, through the agency of lamellar thickness as assessed by low-frequency Raman spectroscopy. The effect of cooling rate on melting point is also explained in terms of variation of supercooling. The implications of these effects together with considerations of surface and interior nucleation and sample size are discussed for the industrial processing of polyethylene.     

Effect of PMR‐POI on the melt behavior and isothermal crystallization of poly(phenylene sulfide)

The crystallization behavior of neat PPS and PPS in blends with PMR‐POI prepared by melt mixing were investigated by differential scanning calorimetry (DSC). It was found that POI was an effective nucleation agent of the crystallization for PPS. The enthalpy of crystallization of PPS in the blends increased compared with that of neat PPS. During isothermal crystallization from melt, the dependence of relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of POI causes an increase in the overall crystallization rate of PPS; it also changed the mechanism of nucleation of the PHB crystals from homogeneous nucleation to heterogeneous nucleation. The equilibrium melting temperature of PPS and PPS/POI blends were determined. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PPS in the composite is due to the decrease in surface energy of the extremity surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 436–442, 2002     

Crystallization of oriented isotactic polypropylene (iPP) in the presence of in situ poly(ethylene terephthalate) (PET) microfibrils

The present article reports the nonisothermal crystallization process and morphological evolution of oriented iPP melt with and without in situ poly(ethylene terephthalate) (PET) microfibrils. The bars of neat iPP and PET/iPP microfibrillar blend were fabricated by shear controlled orientation injection molding (SCORIM), which exhibit the oriented crystalline structure (shish-kebab), especially in the skin layer. The skin layer was annealed at just above its melting temperature (175 °C) for a relatively short duration (5 min) to preserve a certain level of oriented iPP molecules. It was found that the existence of ordered clusters (i.e. oriented iPP molecular aggregates) leads to the primary nucleation at higher onset crystallization temperature, and formation of the fibril-like crystalline morphology. However, the overall crystallization rate decreases as a result that the relatively high crystallization temperature restrains the secondary nucleation. With the existence of PET microfibrils, the heterogeneous nucleation distinctly occurs in the unoriented iPP melt and results in the increase of crystallization peak temperature and overall crystallization rate, for the first time, we observed that the onset crystallization temperature has been enhanced further with addition of PET microfibrils in the oriented iPP melt, indicating the synergistic effect of row nucleation and heterogeneous nucleation under quiescent condition.     

三官能环氧树脂在聚乳酸交联挤出发泡中的应用

将三官能团环氧树脂作为交联剂用于聚乳酸（PLA）的挤出化学发泡成型,研究了三官能环氧树脂含量对PLA熔融结晶性能、交联度、熔体强度的影响以及对PLA化学挤出发泡试样的泡孔形态的影响。结果表明,随着三官能环氧树脂含量的增加,冷结晶温度提高,且添加三官能环氧树脂后熔融峰由单峰变成双峰,结晶峰面积、熔融峰面积以及结晶度都是先增加后减少的趋势;PLA体系的交联度和熔体强度的显著提高随着三官能团环氧树脂的增加;PLA体系泡孔破裂减少,开孔率减少,泡孔尺寸先减小后增大;较佳挤出机头温度为170~175 ℃。     

PE-HD/纳米SiO2杂化材料的等温结晶行为的研究

通过熔融接枝反应将乙烯基三甲氧基硅烷接枝到高密度聚乙烯(PE-HD)分子链上,以四乙氧基硅烷为前驱体,加入接枝的PE-HD中,通过溶胶－凝胶法制备了PE-HD/纳米SiO2杂化材料。用差示扫描量热法研究了纳米SiO2 对PE-HD等温结晶行为的影响。结果表明,随着结晶温度的提高,PE-HD和PE-HD/纳米SiO2杂化材料等温结晶峰明显右移,说明结晶所用时间延长,结晶速率下降;纳米SiO2在PE-HD中起到异相成核的作用,使PE-HD/纳米SiO2的结晶速率比PE-HD的大。等温结晶动力学研究表明,随着结晶温度的提高,两种材料的半结晶期都有所延长,且PE-HD/纳米SiO2杂化材料比PE-HD延长的幅度更大。     

The phase diagram and morphology of blends of poly(vinylidene fluoride) and poly(ethyl acrylate)

The phase diagram and crystallization behaviour of the polymer blend system consisting of poly(vinylidene fluoride) (PVF₂) and poly(ethyl acrylate) (PEA) have been examined. The melt exhibits phase separation upon heating to 10°C–50°C above the melting point of the PVF₂, depending on the composition. The cloud point and equilibrium melting point curve (for α-PVF₂) intersect at about 180°C and a composition of 50% (by weight) PVF₂. The polymer-polymer interaction parameter, χ, was calculated from the equilibrium melting point depression data and found to be −0.16 (at 170°C). Spherulite growth rate data have been measured as a function of composition and temperature. Assuming regime II crystallization a value of the product of the surface free energies of the α-PVF₂ crystals was calculated to be 4.4 × 10⁻⁴J²m⁻⁴. In blends crystallized from the one phase melt the texture of spherulites becomes more open and the spherulite extinction ring spacing (due to lamaller twist) becomes larger with increasing crystallization temperature. In addition the ring spacing increases with PEA content at constant crystallization temperature.     

Crystallization kinetics and morphology of poly(trimethylene terephthalate)

In this work, the isothermal crystallization kinetics of polytrimethylene terephthalate (PTT) was first investigated from two temperature limits of melt and glass states. For the isothermal melt crystallization, the values of Avrami exponent varied between 2 and 3 with changing crystallization temperature, indicating the mixed growth and nucleation mechanisms. Meanwhile, the cold crystallization with an Avrami exponent of 5 indicated a character of three-dimensional solid sheaf growth with athermal nucleation. Through the analysis of secondary nucleation theory, the classical regime I→II and regime II→III transitions occurred at the temperatures of 488 and 468 K, respectively. The average work of chain folding for nucleation was ca. 6.5 kcal mol⁻¹, and the maximum crystallization rate was found to be located at ca. 415 K. The crystallite morphologies of PTT from melt and cold crystallization exhibited typical negative spherulite and sheaf-like crystallite, respectively. Moreover, the regime I→II→III transition was accompanied by a morphological transition from axialite-like or elliptical-shaped structure to banded spherulite and then non-banded spherulite, indicating that the formation of banded spherulite is very sensitive to regime behavior of nucleation.     

Morphology and melt crystallization of poly(L‐lactide) obtained by ring opening polymerization of L‐lactide with zinc catalyst

The morphology and melt crystallization of zinc catalyzed poly(L ‐lactide) (PLLA) were investigated by using differential scanning calorimetry (DSC), polarized optical microscopy, and scanning electron microscopy. Isothermal melt crystallization performed at 95–135°C showed that the morphology depends on the degree of supercooling, as illustrated by crystallite perfection and lamellar thickening behaviors. Double melting peak was observed on DSC thermograms and attributed to the melt‐recrystallization mechanism, small and imperfect crystals becoming gradually more stable ones. Circumferential and hexagonal cracks were detected in PLLA spherulites, which were formed during melt‐crystallization at 135°C and quenching in liquid nitrogen. Rhythmic growth and thermal shrinkage are suggested to be the two main factors accounting for the formation of periodic cracks. Spherulite growth rates of PLLA were evaluated by using combined isothermal and nonisothermal procedures, and were analyzed by the secondary nucleation theory. The maximum growth rate reached 9.1 μm/min at 130°C. The temperature range investigated (120–155°C) belongs to the Regime II of crystallization. The value of U* was found to be 1890 cal/mol, instead of 1500 cal/mol commonly used in literature, and K_g and σ were estimated to be 3.03 × 10⁵ K² and 1.537 × 10^?4 J/m², respectively. As a result, no distinct difference between PLLA catalyzed by zinc metal and those prepared with stannous octoate catalyst exists in this work. POLYM. ENG. SCI., 46:1583–1589, 2006. © 2006 Society of Plastics Engineers.     

Crystallization kinetics and nucleation activity of silica nanoparticle-filled poly(ethylene 2,6-naphthalate)

Silica nanoparticle-filled poly(ethylene 2,6-naphthalate) (PEN) composites were melt-blended to improve the mechanical and rheological properties of PEN. The melt viscosity and total torque values of the composites were reduced by the silica content. The crystallization exothermic peak shifted to a higher temperature, and the overall crystallization time was reduced by increasing the silica content. Non-isothermal crystallization kinetics was analyzed using the Ozawa and Avrami theories, and a combined method. The combined method was successful in describing the non-isothermal crystallization of these composites. The crystallization activation energy calculated using Kissinger's method was reduced, and the spherulite growth rate increased, with increasing silica content.A study of the nucleation activity, which indicated the influence of the filler on the polymer matrix, revealed that the fumed silica nanoparticles had a good nucleation effect on PEN.     

Melt crystallization of syndiotactic polypropylene in nanolayer confinement impacting structure

Layer multiplying coextrusion technique was used to fabricate films with hundreds of alternating layers of a crystallizable polymer, syndiotactic polypropylene (sPP), and an amorphous polymer, polycarbonate (PC). Atomic force microscopy and wide-angle X-ray scattering revealed the absence of any oriented crystal morphology of sPP in the extruded layered films. An approach of isothermal melt recrystallization of sPP nanolayers revealed the formation of oriented lamellae under the rigid confinement of hard glassy PC layers. X-ray scattering data showed that sPP crystallized as stacks of single crystal lamellae oriented parallel to the layers at high crystallization temperatures. As the crystallization temperature decreased, on-edge lamellar orientation was preferred. Formation of in-plane lamellae was attributed to heterogeneous bulk nucleation, while nucleation of on-edge lamellae was initiated at substrate interface. It was observed that as the layers thickness reduced, the orientations of both in-plane and on-edge lamellae became sharper.Detailed analysis of crystal orientations in 30 and 120 nm sPP layers was carried out. Melt recrystallization of 30 nm layers revealed formation of in-plane lamellae above 90 °C and mainly on-edge lamellae below 70 °C. At intermediate temperatures, formation of mixed crystals was reported. In 120 nm layers, crystallization temperature of 100 °C was required to form in-plane crystals, while on-edge lamellae were formed below 90 °C.We also investigated crystallization onset for on-edge and in-plane lamellar nucleation. Although, the two crystal fractions were significantly affected as a function of crystallization temperature, it was noticeable that both crystal habits were initiated at the same time. The results suggested that the relative growth rates of in-plane and on-edge crystal orientations was responsible for different fractions of the two crystal orientations at a given crystallization temperature.Oxygen transport properties of melt recrystallized sPP layers were measured. When the melt recrystallization temperature increased from 85 to 105 °C in 120 nm sPP layers, at least one order of magnitude enhancement in the barrier properties was observed. It was evident from the X-ray data that the amount of in-plane crystal fraction increased with increasing crystallization temperature. In-plane crystals acted as impermeable platelets to oxygen flux resulting in improved gas barrier properties. A similar effect was observed in 30 nm sPP layers over a temperature range of 60-105 °C. A correlation between in-plane crystal fraction and the oxygen permeability was obtained from X-ray and oxygen transport data analysis. It was shown that the permeability decreased exponentially with increasing in-plane crystal fraction.     

滑石粉、碳酸钙填充聚丙烯复合材料等温结晶行为的对比研究

用熔融共混法分别制备了聚丙烯（PP）/滑石粉、PP/碳酸钙(CaCO3)复合材料,用差示扫描量热法(DSC)考察了PP及其复合材料的等温结晶过程,并用Avrami方程对纯PP及PP/滑石粉、PP/CaCO3复合材料的等温结晶动力学行为进行了分析。结果表明,PP、PP/滑石粉及PP/CaCO3复合材料的Avrami指数均小于2.3,存在均相成核和异相成核双重成核机理,且其结晶速率常数和结晶速率均随着结晶温度的升高而减小;在该体系中,滑石粉对基体PP有明显的异相成核作用,使PP的结晶速率加快、结晶时间缩短;而CaCO3则没有明显的异相成核作用。