Crystal morphology and transcrystallization mechanism of isotactic polypropylene induced by fibres: interface nucleation versus bulk nucleation

Using polarized optical microscopy (POM) equipped with a hot stage, morphological investigations of an isotactic polypropylene (iPP) matrix, induced by a homogeneous iPP fibre and heterogeneous pure/modified nylon 6 fibres, were carried out. With respect to transcrystallization related to heterogeneous nucleation on the surface of the fibre, the nucleation mode was found to be different for iPP fibres and nylon 6 fibres. An iPP fibre can serve as a macroscopic linear nucleus, similarly to the shish‐type structure formed in stress‐induced crystallization, to induce kebab‐like growth of lamellae, whereas numerous closely packed spherulites along nylon 6 fibres resulted in macroscopic transverse growth to form a transcrystallite owing to the limitation along the fibre axis. The difference in nature between these two transcrystallites can be further demonstrated by their optical characters related to the lamellar arrangement inside the transcrystallite. As for homogeneous iPP composites, the formation of transcrystallites results from lattice matching, in consideration of the same chemical structure and lattice parameters between fibre and matrix. The incorporation of calcium chloride into a nylon 6 fibre—to destroy its crystal structure—confirmed the role of lattice matching between nylon 6 fibre and iPP matrix. The addition of atactic polypropylene (aPP) in order to enhance the nucleation ability of the iPP matrix also greatly weakened transcrystallization. Our work demonstrates that transcrystallization is just a matter of competition between interface nucleation and bulk nucleation, namely, if interface nucleation is faster than bulk nucleation, transcrystallization will develop. If not, it will be suppressed. Copyright © 2006 Society of Chemical Industry     

Morphologies of iPP induced by its partially carbon-coated homogeneity fibers

Homogeneity fiber/matrix composites of isotactic polypropylene (iPP) were prepared with both partially carbon-coated and non-carbon-coated iPP fibers. Their morphologies produced by melt recrystallization were studied by means of polarized optical microscopy. The results show that through vacuum evaporating a thin carbon film partially on the surface of iPP fiber, the nucleation ability of the molten iPP matrix during the course of recooling has been enhanced tremendously. The early formation and high density of the iPP row nuclei formed along the partially carbon-coated iPP fibers lead to the formation of an apparent iPP transcrystalline zone in the vicinity of its precoated fiber. The high nucleation ability of the carbon-coated iPP fiber towards its homogeneity matrix may originate from the surface fixing effect of the vacuum evaporated carbon layer on the polymer samples.     

The effects of transcrystalline interphase in advanced polymer composites

Surface-induced transcrystallization in fibers has been reported in some advanced polymer composites. It is believed that transcrystalline interphase may affect stress transfer efficiency between the reinforcing fiber and the matrix. In this study, attempts were made to examine the effects of transcrystallinity on composite performance, particularly on fiber-matrix interfacial bond strength, and to investigate possible attributes of transcrystallization. Three polymer resins, poly(etherketoneketone) (PEKK), poly(etheretherketone) (PEEK), and poly(phenylenesulfide) (PPS), and four types of fiber, polyacrylonitrile (PAN)-based AU-4 (untreated AS-4) carbon, pitch-based carbon, poly (p-phenylene terephthalamide) (PPDT) aramid, and E-glass were used. It was found that PPDT aramid and pitch-based carbon fibers induce a transcrystalline interphase in all three polymers because of an epitaxial effect. Under certain conditions, transcrystallization was also observed in PAN-based carbon and E-glass fibers, which may be partially attributed to the thermal conductivity mismatch between the fiber and the matrix. Plasma treatment on fiber surface showed a negligible effect on inducing transcrystallization, whereas solution-coating of PPDT on the fiber surface showed a positive effect. The Microdebonding test, which measures the interfacial bond strength between the fiber and the matrix, consistently showed more than 40% increments for various single filament systems with transcrystalline interphase versus without. However, the effects of transcrystallinity on the interfacial bond strength appeared to decrease as the fiber content increased in composites.     

碳纤维增强聚酰胺6复合材料的结晶行为研究

通过偏光显微镜和差示扫描量热仪(DSC)研究了碳纤维(CF)和滑石粉对聚酰胺6(PA6)结晶行为的影响。结果表明,CF的加入在PA6和CF的界面诱发横晶,CF和滑石粉在PA6基体中起到了异相成核作用,改变PA6的成核机理和晶体生长方式,提高了起始结晶温度和结晶速率。结晶速率随普等温结晶温度的升高而下降。当冷却速率增大时,起始结晶温度下降,结晶度增大。     

Fiber reinforced polypropylene: Influence of iPP molecular weight on morphology,crystallization, and thermal and mechanical properties

The influence of molecular weight and its distribution on the nucleation density, crystallization, thermal and mechanical behavior of isotactic polypropylene based composites has been investigated. The composites were prepared by compression molding. The ability of carbon and Kevlar fibers to nucleate the polypropylene has been studied during isothermal and nonisothermal crystallization, by optical microscopy and differential scanning calorimetry (DSC), as function of crystallization temperature T_c and iPP molecular weight. Two extreme crystallization conditions were tested: quenching and slow crystallization to obtain crystals and amorphous phases of different structure. The ability of fibers to enhance mechanical properties in polypropylene based composites was examined by tensile tests at room temperature. It was found that nucleation density, crystallization parameters, and the results of tensile tests strongly depend on the molecular weight M w of iPP, molecular weight distribution, and thermal history of polypropylene. The numerical values of the nucleation density have been found to strongly depend on the nature of fiber. In fact, Kevlar fiber has shown a better nucleating ability than carbon fiber. The results of tensile tests have been related to the sample morphology. The analysis of fractured specimens also provided useful information about fiber-matrix adhesion.     

Thermal and chemical effects of nucleating agents on α, β, γ-polymorphism of isotactic polypropylene

Isotactic polyprpylene (iPP) occurs in several crystalline forms, denoted as f (monoclinic), g (hexagonal), and n (orthorhombic) phases. Hot-stage microscopy, differential scanning calorimetery, and wide-angle X-ray diffraction were used to investigate the influence of thermal treatment and nucleating agents on the morphology of iPP matrices. The tendency of glass fiber (GF) and Kevlar aramid fiber (KF) to induce transcrystallinity in different iPP matrices was evaluated. The f form was present in all iPP specimens treated by different nucleating agents at different crystallization temperatures (Tc). The g and n forms (impure) were found only in iPP specimens that were treated with g -nucleating agent and n - nucleating agent, respectively. Development of transcrystallization was found to depend on the type of fiber used, nucleating agents, and Tc. It was observed that the crystallinity content, obtained by applying different thermal treatments (slow cooling or quenching), gave rise to different morphologies of iPP matrices.     

Influence of crystallization temperature on the morphologies of isotactic polypropylene single-polymer composite

The supermolecular structures of iPP fiber/matrix composites as a function of crystallization temperature were studied by means of optical microscopy. The results show that, even though partial melting of the iPP fibers is in favor of initiating the β-iPP crystal growth, the interfacial morphology of iPP single-polymer composites induced by its own fiber depends strongly on the crystallization temperature. It was found that transcrystalline structures of negative radial β_III-iPP or banded β_IV-iPP can be produced within the crystallization temperature range 105-137 °C, while transcrystallization zone of pure negative radial α_II-iPP crystals is observed at higher crystallization temperature, e.g. 141 °C. On the other hand, the surrounding iPP spherulites grown from the bulk are composed of α-iPP in the whole crystallization temperature range. However, the optical character of the spherulites is controlled by the thermal condition.     

Crystallization of poly(etheretherketone) (PEEK) in carbon fiber composites

The tendency of carbon fiber to nucleate the zation of poly(etherettterlcetone) (PEEK) has been evaluated by DSC and other techniques. As the carbon fiber content was increased, the supercooling necessary for PEEK crystallization decreased. The repeated melting (at 396°C) of the same PEEK sample results in a decrease of the number of nuclei for crystallization. At equivalent thermal histories, PEEK with carbon fiber was found to have a higher nucleation density than PEEK itself. The surface of carbon fibers and nuclei in the PEEK matrix compete for crystallization growth. As the holding time in melt was increased, the number of matrix spherulites formed on cooling decreased, hence a more pronounced transcrystalline region was developed. Correspondingly, the composites preheated in the melt for 100 min showed about two times the transverse tensile strength and strain-to-failure of those preheated for only 30 min. Corresponding fracture surface produced in tension showed that the former samples had a greater matrix adhesion to the carbon fiber than the latter. A strong interfacial bond is thus developed by crystallization on carbon fiber surface. Destroying nuclei in the PEEK matrix by long preheating enhances crystallization on the carbon fiber.     

Influence of surface morphology of the kraft pulp fibers on the growth of the transcrystalline layer of polypropylene

The objective of this study was to evaluate the influence of the wood fiber surface on the crystallization behavior of thermoplastic polymers. Unbleached and bleached kraft pulp fibers were used for this study with 100% polypropylene (PP), 95% PP/5% maleic anhydride polypropylene (MAPP), and 100% MAPP at 150°C. Nuclei were induced at the ends of the fibers and on damaged surfaces while poor crystallization behavior was observed on the fiber surfaces using 100% PP. Enhanced MAPP induced transcrystallization on the wood fiber surfaces; the nucleation density also increased with the addition of MAPP. Oxygen/carbon (O/C) ratios of smooth surfaces, damaged surfaces, and the ends of wood fibers also indicated that the oxidation process of both wood fiber and thermoplastic polymer affected the crystallization process without MAPP addition. It was observed that the MAPP played a role in increasing numbers of nuclei on the linear fiber surface to induce transcrystallization. Dynamic mechanical properties increased 52% with 100% MAPP compared to the use of 100% PP. Therefore, the increased thickness of transcrystalline layer and nucleation density on the surface of wood fiber positively correlated with the dynamic mechanical properties of wood fiber‐plastic composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrospun-fiber induced transcrystallization of isotactic polypropylene matrix

To reveal the influences of fiber diameter and characteristics on the surface-induced matrix crystallization, four different fibers, i.e. syndiotactic polystyrene (sPS), Nylon 6, and polyhydroxyamide (PHA) and poly(p-phenylene benzobisoxazole) (PBO) fibers, were used to study their nucleating abilities towards isotactic polypropylene (iPP) matrix. Among them, micron-sized PBO fibers were obtained from the supplier, whereas submicron-sized fibers of sPS, Nylon 6 and PHA were prepared by the solution electrospinning process developed in this laboratory. To resolve the observation difficulty due to the fast nucleation rate and crystal growth at high supercooling degrees (>60 °C), a high speed camera was mounted on the polarized optical microscope equipped with a hot stage to successfully snapshot the corresponding processes at various crystallization temperatures (T_c) in the range of 96-120 °C. For all the active fibers, only α-form iPP transcrystallites were observed at the fiber/matrix interface. Two crucial parameters were proposed for characterizing the fiber nucleating ability, i.e. the interfacial free energy difference (Δσ) based on the heterogeneous nucleation from a thermodynamic point of view, and the maximum temperature for transcrystalline layer observed (T_max) based on a kinetic consideration. Values of Δσ for different fibers were derived on the basis of the tertiary nucleation taking place in the selective “grooves” at the fiber surface. It was found that the nucleating rate of sPS fibers was scaled with the fiber diameter, and Δσ showed a negligible diameter dependence, but T_max slightly increased with increasing fiber diameter. For all the fibers investigated, an intimate relation between the Δσ and T_max was derived and used to compare their nucleating abilities.     

Enhanced β‐crystal formation of isotactic polypropylene under the combined effects of acid‐corroded glass fiber and preshear

The acid‐corroded glass fiber (GF)/isotactic polypropylene (iPP) composite was injection molded by mixing–injection molding (MIM). Through this method, preshear can be imposed on melt during mix–plasticization process. The crystalline structure across the thickness direction of the injection‐molded bars was investigated by wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). It was unexpectedly found that, in core region, the acid‐corroded GF/iPP sample has the highest content of β‐form crystals, followed by uncorroded GF/iPP and neat iPP. Additionally, the crystalline morphology was investigated by polarized optical microscopy (POM) and scanning electron microscopy, and the results showed that β‐transcrystallization is preferably present in the acid‐corroded GF/iPP system. Confirmed by POM and DSC, the acid‐corroded GF shows strong β‐nucleation ability to iPP under static condition. Combined with the main features of MIM, three β‐nucleation origins in the acid‐corroded GF/iPP system under injection molding condition are proposed: (1) precursors induced by preshear in the barrel, (2) row‐nuclei induced by local shear, and (3) the acid‐corroded GF nuclei. POLYM. COMPOS. 34:1250–1260, 2013. © 2013 Society of Plastics Engineers     

碳纤维表面阴离子接枝尼龙6对CF/PA6复合材料界面形态的影响

研究了碳纤维(CF)表面阴离于接技尼龙6(PA6)对CF/PA 6复合材料界面形态的影响,考察了纤维表面、结晶温度对CF/PA 6复合材料界面形成横晶的影响.结果表明在低于初始结晶温度至接近熔点范围内,PA6在未接枝与接枝CF表面均可以形成横晶,结晶温度低形成的横晶不致密、不完整,纤维诱发横晶的能力小,结晶温度高形成的横晶完整而致密,纤维诱发横晶的能力大.在相对较低的结晶温度下,接枝CF比未接枝CF具有较高的诱发横晶能力,同时诱发的横晶致密度高及完整性好.     

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.     

Recrystallization behavior of β‐isotactic polypropylene in homogeneous and heterogeneous matrix–fiber composites

β‐isotactic polypropylene (β‐iPP) cylindritic crystals were produced in homogeneous iPP fiber–matrix composites and heterogeneous polyamide (PA)–iPP fiber–matrix composites under different sample preparation conditions. The melt recrystallization behaviors of the β‐iPP crystals obtained in the homogeneous and heterogeneous composites were studied by optical microscopy. The experimental results show that, by heating the sample to 180 °C, the birefringence contributed by the iPP crystals in both α‐ and β‐forms disappears completely. During the cooling process, the β‐iPP crystals in the homogeneous composite appear again, while the iPP in the heterogeneous composite crystallizes in its α‐form. This demonstrates the different origins of the β‐iPP cylindrites in the homogeneous and heterogeneous composites. While the β‐iPP cylindrites in the heterogeneous composite are associated with the sample preparation procedure, the β‐iPP cylindrites in the homogeneous composite are produced by recrystallization of the molten but incompletely relaxed iPP fibers. In situ observation of the melt recrystallization process shows that the molten iPP oriented fibers crystallize first during the cooling process at relatively higher temperature in the α‐form. Abundant randomly dispersed β‐iPP nuclei formed at the surface of the recrystallized iPP fibers, which generate the β‐iPP cylindrites. Copyright © 2012 Society of Chemical Industry     

Preparation and crystallization behavior of UHMWPE/LLDPE composites

UHMWPE fiber reinforced LLDPE composites were prepared to develop the impact resistant materials. The crystallization kinetics of LLDPE with UHMWPE fiber was investigated to understand the interfacial adhesion and composite performance. The crystallization behavior of LLDPE depends on the crystallization temperature and existence of UHMWPE fiber. LLDPE matrix crystallization was affected by the inclusion of UHMWPE fiber via preceded transcrystallization on the fiber surface. The interfacial adhesion of composites was changed by cooling rate control with different crystallization behavior. Received: 29 August 1997/Revised version: 7 November 1997/Accepted: 13 November 1997     

The effects of a nucleating agent and of fibers on the crystallization of nylon 66 matrices

Crystallization from the melt of nylon 66 in the presence of carbon fiber, aramid fiber, or nucleating agent was studied using differential scanning calorimetry (DSC) and hot stage microscopy. The use of the nucleating agent resulted in an increase in crystallization rate and a decrease of induction time under both isothermal and nonisothermal conditions. The fibers were found to behave like a giant nucleating site producing a uniform transcrystalline layer having morphology and crystallization kinetics different from those of the bulk matrix. The influence of the cooling rate on the process of nonisothermal crystallization was analyzed, and the values of activation energy, calculated from the cooling rate—crystallization temperature relationship, appeared to be higher for the nucleated and for the reinforced nylon compared with that of the neat nylon 66. This implied that the presence of fibers or nucleating agent led to the development of a more ordered structure, which required a larger amount of energy for crystallization.     

Crystallization and fiber/matrix interaction during the molding of PEEK/carbon composites

The objective of this work was to investigate the effects of molding conditions (molding temperature, residence time at melt temperature, and cooling rate) on the crystallization behavior and the fiber/matrix interaction in PEEK/carbon composites made from both prepreg and commingled forms. In order to investigate the crystallization behavior of the PEEK matrix, the molding process was simulated by differential scanning calorimetric analysis, DSC. The results show that the prepreg and commingled systems do not have the same matrix morphology; prepreg tape was found to be at its maximum of crystallinity, whereas the commingled system was found to be only partially crystalline. The results show that processing must be carried out at a temperature sufficiently high to destroy the previous thermal history of the PEEK matrix; this is an essential requirement to produce efficient fiber/matrix adhesion in the commingled fabric system. Optical microscopic observations also suggest that matrix morphology near the fibers is dependent on the melting conditions; a well-defined transcrystalline structure at the interface is observed only when the melt temperature is sufficiently high. However, the high temperature of molding can easily result in degradation of the PEEK matrix such as chain scission and crosslinking reactions. Thermal degradation of the matrix during processing is found to affect the crystallization behavior of the composites, the fiber/matrix adhesion, and the matrix properties. This effect is more important in the case of a commingled system containing sized carbon fibers because the sizing agent decomposes in the molding temperature range of PEEK/carbon composites. This produces a decrease of the matrix crystallinity and an elimination of the nucleating ability of the carbon fibers. A transition between cohesive and adhesive fracture is observed when the cooling rate increases from 30°C/min to 71°C/min for the composite made from the commingled fabric. This critical cooling rate is found to closely correspond to a change in the mechanism of crystallization of the PEEK matrix.     

Interfacial crystallization and its mechanism in in-situ dynamically vulcanized iPP/POE blends

The effect of in-situ crosslinking of poly (ethylene-co-octene) (POE) rubber phase on the interfacial crystallization of isotactic polypropylene (iPP) in dynamically vulcanized iPP/POE blends was studied. The results showed that in situ crosslinking of POE obviously increased the interfacial crystallization of iPP in the dynamically vulcanized blends, comparing with that of pure iPP and the unvulcanized blend. The interfacial crystallization of iPP was further increased with the increase in crosslink degree. After annealing, the obvious interfacial crystallization was still obtained in the blend with high crosslink degree. Based on the fluctuation assisted nucleation mechanism in solution blended iPP/polyolefin block copolymer (OBC) blends, we proposed for the first time the interfacial crystallization mechanism in dynamically vulcanized blends: the oriented chains of iPP formed by concentration fluctuation at the interface during phase separation or shearing stress during melt mixing can be maintained because of the in situ crosslinking of POE phase, resulting in the enhancement of nucleation density at the iPP/POE interface. Our study proposes a new interfacial crystallization mechanism, and provides guidance for the preparation of high performance thermoplastic vulcanizates (TPVs) product by tailoring the interfacial crystallization of TPVs.     

Morphology and mechanical behavior of isotactic polypropylene (iPP)/syndiotactic polypropylene (sPP) blends and fibers

The crystallization morphologies and mechanical behaviors of iPP/sPP blends and the corresponding fibers were investigated in the present work. For all the investigated iPP/sPP blends, the starting crystallization temperature of sPP during cooling process was significantly increased with increasing iPP content. The iPP/sPP blends are strongly immiscible at the conventional melt processing temperatures, in consistence with the literature results. As isothermally crystallized at 130 °C, sPP still keeps melt state, while iPP component is able to crystallize and the spherulites become imperfect accompanied by decreasing of the crystallite size as sPP content increases. The addition of sPP decreases the crystallinity of iPP/sPP blends and fibers. The storage modulus, E′, of the iPP/sPP blends is higher than that of sPP homopolymer in the temperature range from −90 to 100 °C. The iPP/sPP fibers can be prepared favorably by melt-spinning. As sPP content exceeds 70%, the elastic recovery of the iPP/sPP fibers is approximately equal to that of sPP homopolymer fiber. The drawability of the as-spun fiber of iPP/sPP (50/50) is better than that of sPP fiber, which improves the fiber processing performance and enhances the mechanical properties of the final product. The drawn fiber of sPP presents good elastic behavior within the range of 50% deformation, whereas the elastic property of the iPP/sPP (50/50) fiber slightly decreases, but still much better than that of iPP fiber.     

Effects of fibers on the crystallization of poly(phenylene sulfide)

The isothermal crystallization of unreinforced poly(phenylene sulfide) (PPS) and PPS filled with glass, carbon, and aramid fibers was studied by differential scanning calorimetry. The Avrami exponent and rate constant are reported, but the crystallization half-times were used to compare the effects of different fibers on the rate of PPS crystallization. The aramid and carbon fibers decreased the crystallization half-time with the aramid fiber having the most pronounced effect. The glass fibers affected the crystallization half-time only at the higher crystallization temperatures. The aramid filled PPS exhibited anomalous degree of crystallinity behavior in that the degree of crystallinity passed through a minimum as a function of temperature. The other systems all exhibited increasing degree of crystallinity with increasing crystallization temperature. Finally, the Avrami plot for the aramid filled PPS is not linear, and the data are fitted better with two linear regions indicating that two types of crystallization processes may be present.