Transcrystallization of PTFE fiber/PP composites. II. Effect of transcrystallinity on the interfacial strength

It has been found that transcrystallinity of polypropylene (PP) develops easily on the polytetrafluoroethylene (PTFE) fiber surface in spite of the low surface energy of the fiber. Effect of the transcrystallinity on the interfacial strength has been extensively investigated using a single-fiber pull-out test. By controlling the crystallization temperature, range 25–130°C, the thickness of the transcrystalline layer varied from 0 to 175 μm for thick specimens, ca. 1 mm thick. Measurements of the adhesive fracture energy, the interfacial shear strength and the frictional stress were carried out for specimens with different embedded fiber lengths. Results show that interfacial strength and fracture energy are independent of the transcrystalline thickness. The calculated value of interfacial shear strength is 3.6 MPa, and the fracture energy for debonding is 2.1 J/m². The presence of transcrystallinity does not promote the level of adhesion in PTFE/PP composites. However, the frictional stresses at the debonded fiber/matrix interface increase with transcrystalline thickness. It is attributed to the residual stresses which arise from shrinkage when specimens are cooled from crystallization temperature to room temperature. © 1996 John Wiley & Sons, Inc.     

Thermal and crystallization studies of nano-hydroxyapatite reinforced polyamide 66 biocomposites

The thermal and crystalline behaviour of nano-hydroxyapatite (n-HA) reinforced polyamide 66 (PA66) biocomposites was studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). The thermal properties of PA66 and n-HA/PA66 composites were analysed by TG. The effect of hydroxyapatite on the melting and crystallization of PA66 was evaluated by DSC. DSC measurements exhibited an increase in the crystallization temperature, however, decrease in crystallinity with the addition of n-HA to the PA66 matrix, which was attributed to the hydrogen bonds between the n-HA surface and polyamide 66 molecules. With increase of n-HA content, the melting peak of the PA66 component shifted to higher temperature, suggesting constrained melting. The addition of n-HA to PA66 played the role of nucleating agent and enhanced the crystallization rate. Non-isothermal parameter a measured by Liu method varies from 1.13 to 1.18, from 1.02 to 1.07, and from 1.18 to 1.21 for PA66, 30 wt% n-HA/PA66 and 40 wt% n-HA/PA66, respectively, and the values of K_(T) systematically increase with rise in relative degree of crystallinity.     

Structure and Properties of β-Polypropylene Reinforced by Polypropylene Fiber and Polyamide Fiber

Matrix/fiber composites of β-form isotactic polypropylene(iPP) matrix and α-iPP or PA6 fibers were prepared by laminating technique under different preparation temperatures. The mechanical properties and interfacial morphologies of these composites were studied by tensile test, optical microscopy and scanning electron microscopy, respectively. The experimental results show that the tensile yield load and tensile modulus of β-iPP/PA6 matrix/fiber systems increased significantly at the expense of elongation at break. These mechanical properties show essentially no dependence on the sample preparation temperature. On the other hand, the mechanical properties of iPP matrix/fiber single polymer composites depend strongly on the sample preparation temperature. At low sample preparation temperature, e.g., 172 ℃, the solid α-iPP fiber induces α-iPP crystallization, leading to the formation of α-iPP transcrystalline layer around the fiber. This results in a remarkable increment of the tensile yield load and tensile modulus. The elongation at break is also much better than that of the iPP/PA6 matrix/fiber system. It reflects a better interfacial adhesion of the single polymer composite compared with the iPP/PA6 composite. At higher sample preparation temperature, e.g., 174 ℃ or 176 ℃, the partial surface melting of the oriented fiber allows interdiffusion of iPP molecular chains in the molten fiber and matrix melt. The penetration of matrix chains into the molten iPP fiber results in some iPP molecular chains being included partially in the recrystallized fiber and the induced β-transcrystalline layers. This kind of configuration leads to an improvement of interfacial adhesion between the fiber and matrix, which causes a simultaneous increase of the tensile yield load, tensile modulus and elongation at break of β-iPP.     

Influence of maleic anhydride-grafted EPDM and flame retardant on interfacial interaction of glass fiber reinforced PA-66

In this paper, the effects of melamine polyphosphate flame retardant (MPP-FR) and maleic anhydride-grafted EPDM (MA-EPDM) on the interfacial interaction of PA66/GF were investigated by means of scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), rheological behavior and mechanical properties. The experimental results demonstrate that MPP-FR and MA-EPDM could effectively improve interfacial interactions between the PA66 and GF. Based on SEM, good interfacial adhesion between PA66 and GF in PA66/GF/FR and PA66/GF/FR/MA-EPDM composites was observed, however, MPP-FR destroyed the PA66 matrix. DMA results show that MPP-FR increased glass transition temperature (T_g) and storage modulus, and lower tan δ, while MA-EPDM showed a little effect on them in PA66/GF/FR/MA-EPDM composite compared with PA66/GF/FR. MPP-FR made PA66 crystallization temperature and the activation energy of the macromolecular segments transport increase clearly, and enhanced crystallization degree of PA66 according to DSC results. These results demonstrate MPP-FR presented the nucleate effect for the crystallization of PA66. At the low shear rate, MPP-FR and MA-EPDM obviously enhanced apparent viscosities of the composites. This is attributed that MPP-FR improved the interfacial interaction of the composites, and MA-EPDM promoted the formation of high molecular weight structures by the reactions between MA and amine groups. All results in this paper were consistent, and showed the good interaction among PA66, GF, MPP and MA-EPDM, which were proved by the mechanical properties of the composites.     

Heterogeneous nucleation of crystallization of high polymers from the melt. I. Substrate-induced morphologies

Melt crystallization of isotactic polypropylene (iPP), poly(ethylene oxide), poly(butene-1), and polycaprolactone in contact with various substrates (mostly polymeric) has been studied by hot stage polarizing microscopy. Nucleating abilities of surfaces have been characterized qualitatively by examining the substrate-induced morphologies of the crystallizing polymer. These morphologies have been classified into three groups, depending on whether the substrate is very active (transcrystallinity), moderately active, or inactive as a nucleating agent. The morphologies observed are temperature-dependent, changing from transcrystalline to spherulitic upon increase of the crystallization temperature. At intermediate temperatures, mixed surface morphologies (transcrystalline plus spherulitic) are observed. The concentration of titanium and aluminum catalytic residues in isotactic polystyrene (iPS) samples can be reduced by two methods, i.e., (a) fractionating the polymer and (b) chelating Ti and Al with acetylacetone. The high nucleating ability of iPS samples in the crystallization of iPP has been shown to be due to the polymer (iPS) itself, and not to Ti and Al residues. Apart from iPS, other polymers (low energy surfaces) have also been found to induce transcrystallinity. From a survey of 43 substrate-crystallizing polymer pairs, conclusions have been drawn which are relevant to the following potential factors in heterogeneous nucleation processes: (a) chemical structure, (b) crystallographic unit cell type, (c) lattice parameters, (d) crystallinity of substrate, and (e) surface energy of substrate.     

Non-isothermal crystallization kinetics and morphology of wollastonite-filled β-isotactic polypropylene composites

To obtain wollastonite-filled β-iPP composites, the wollastonite with β-nucleating surface (β-wollastonite) was prepared through chemical reaction between wollastonite with α-nucleating surface (α-wollastonite) and pimelic acid. The formation of calcium pimelate on the surface of wollastonite was proved using Fourier transform infrared spectrometry and scanning electron microscopy. The crystallization behavior, melting characteristics, non-isothermal crystallization kinetics, and crystalline morphologies of α- and β-wollastonite-filled iPP composites were studied by differential scanning calorimetry and polarizing optical microscopy. It is found that the crystallization peak temperatures of β-wollastonite-filled iPP composites were higher than that of α-wollastonite-filled iPP composites, which indicated that wollastonite with β-nucleating surface has stronger heterogeneous nucleation than that of wollastonite with α-nucleating surface. Although the crystallization temperatures of iPP and iPP composites decreased with increasing cooling rates, α-wollastonite-filled iPP composites mainly crystallized in α-spherulite and β-wollastonite-filled iPP composites formed β-spherulite. In addition, the spherulite size of β-wollastonite-filled iPP composites was smaller than that of α-wollastonite-filled iPP composites. Jeziorny and Mo methods were applicable to study the non-isothermal crystallization kinetics of wollastonite-filled iPP composites. The activation energy (?E) and the nucleation efficiency (EN) of non-isothermal crystallization were calculated by Kissinger method and the equation proposed by Fillon, respectively. The β-wollastonite-filled iPP composites exhibited higher crystallization rate, activation energy, and EN than that of α-wollastonite-filled iPP composites.     

HDPE solution crystallization induced by electrospun PA66 nanofiber

Nanohybrid shish?Ckebab (NHSK), induced by polyamide 66 (PA66) nanofiber, was successfully fabricated in high-density polyethylene (HDPE)/xylene solution via isothermal crystallization. The crystalline morphological features of NHSK were observed by scanning electron microscopy. In the structure of NHSK, PA66 nanofiber serves as shish and HDPE lamellae act as kebabs periodically surrounding the nanofiber. Additionally, it reveals that both HDPE solution concentration and crystallization time have significant effects on the size of HDPE kebab. That is, as the concentration and crystallization time increase, the diameter of the kebab increases. Moreover, when crystallization time further increases, the crystals decorated on PA66 nanofiber exhibit a three-dimensional growth (i.e., aggregate of crystallites) rather than a two-dimensional one (i.e., disk-like lamellae normal to the axis of nanofiber).     

A comparison study on the homogeneity and heterogeneity fiber induced crystallization of isotactic polypropylene

The crystallization behavior of iPP in composites with PET, Nylon-6 and its own fibers under various conditions was studied using an optical microscope equipped with a hot stage. The results show that the nucleation capacity of PET and Nylon-6 fibers towards the iPP matrix is mainly controlled by the shear flow of the iPP matrix during sample preparation. When the composites were prepared at a temperature where the iPP was kept in its supercooled state, the nucleation of iPP on the PET and Nylon-6 fiber surfaces was enhanced due to the shearing of the iPP melts caused by introduction of the fibers. The nucleation was markedly reduced by keeping the composites at the fiber introduction temperature for a short time to relax the shear flow of the iPP matrix. The nucleation of iPP on its own fiber, however, is mainly related to the nature of the iPP fiber itself. No detectable morphological change of iPP on its own fiber can be identified under all thermal conditions used in this study.     

Heterogeneous nucleation of crystallization of high polymers from the melt. II. Aspects of transcrystallinity and nucleation density

In the initial stage of the development of transcrystallinity, nuclei appear sporadically on the substrate. The growth rate and melting temperature of the transcrystalline region are found to be the same as those of spherulites nucleated in the bulk of the polymer. Nucleation densities n_s at the interface, and n_b in bulk, for the crystallization of isotactic polypropylene, poly(ethylene oxide), and poly(butene-1) in contact with various substrates, have been measured by counting the number of spherulites generated. Despite variations in the results from various causes, the quantities n_s and n_s/n_b are useful parameters for characterizing the nucleating ability of various substrates.     

Nucleation activity of nanosized CaCO3 on crystallization of isotactic polypropylene, in dependence on crystal modification, particle shape, and coating

A detailed analysis of the effect of calcium carbonate nanoparticles on crystallization of isotactic polypropylene (iPP) is reported in this contribution. CaCO₃ nanoparticles with different crystal modifications (calcite and aragonite) and particle shape were added in small percentages to iPP. The nanoparticles were coated with two types of compatibilizer (either polypropylene-g-maleic anhydride copolymer, or fatty acids) to improve dispersion and adhesion with the polymer matrix.It was found that the type of coating agent used largely affects the nucleating ability of calcium carbonate towards formation of polypropylene crystals. CaCO₃ nanoparticles coated with maleated polypropylene can successfully promote nucleation of iPP crystals, whereas the addition of nanosized calcium carbonate coated with fatty acids delays crystallization of iPP, the effect being mainly ascribed to the physical state of the coating in the investigated temperature range for crystallization of iPP, as well as to possible dissolution by fatty acids of heterogeneities originally present in the polypropylene matrix.     

Crystallization properties and thermal stability of polypropylene composites filled with wollastonite

The influence of wollastonite (CaSiO₃) content on the crystallization properties and thermal stability of polypropylene (PP) composites was investigated. The results showed that the crystallization temperature, crystallization end temperature and crystallization temperature interval, as well as the degree of crystallinity of the composites, were higher than those of the unfilled PP resin, while the crystallization onset temperature was little changed from that of the unfilled PP resin. The increase of degree of crystallinity for the composites could be attributed to the heterogeneous nucleation of the CaSiO₃ in the PP matrix. The thermal stability increased with increasing filler weight fraction (ϕ_f); the thermal decomposition rate decreased nonlinearly with increasingϕ_f. Finally, the dispersion of the filler particles in the matrix was observed, and the mechanisms of thermal stability and crystallizing behavior were discussed.     

In situ fibrillation of polyamide 6 in isotactic polypropylene occurring in the laminating‐multiplying die

The polyamide 6 (PA6)/isotactic polypropylene (iPP) in situ fibrillation composites are prepared by a novel extrusion die with an assembly of laminating‐multiplying elements (LMEs). The scanning electron micrographs illustrate that the dividing‐multiplying processes in LMEs elongate, break, and stabilize the dispersed PA6 phase in the iPP matrix along the flowing direction (FD). The morphology development of PA6 with different LME numbers greatly affects the rheological properties, crystalline behaviors, and mechanical properties. The dynamic rheological test performed at 195°C shows that the increased spatial restriction of the high‐aspect‐ratio PA6 particles increases the viscoelastic moduli, complex viscosity, and relaxation time. The crystalline analysis reveals that the heterogeneous nucleation becomes predominant and the transcrystalline morphology is observed in those samples produced by more LMEs. The tensile tests indicate that both, breaking strength and elongation, enhanced simultaneously because of the fibrillation of dispersed phase and the improvement in interfacial adhesion between the fibers and the matrix. Copyright © 2009 John Wiley & Sons, Ltd.     

The effect of the addition of polypropylene grafted SiO2 nanoparticle on the crystallization behavior of isotactic polypropylene

The crystallization behavior of isotactic polypropylene (iPP)/silica particle (SiO₂, 26 nm) nanocomposite has been investigated. In addition to the non surface-modified SiO₂, iPP grafted SiO₂ was synthesized and adopted to this study with an aim to understand the role of grafted polymer chain on the crystallization process. The crystallization rate of non surface-modified iPP/SiO₂ composite stays constant up to 1 vol%. It suggests the very weak nucleation ability of nano-sized silica particle. While large acceleration effect was observed for iPP-grafted SiO₂/iPP composite. The spherulite density increased with increasing SiO₂ contents, and more interestingly, the spherulite growth rate also increased. This finding leads to the conclusion that the grafted iPP chain has a plasticizing effect that reduces the chain entanglements at the interface. Further increase in SiO₂ contents, the crystallization rate, the spherulite density, and the spherulite growth rate showed the steep decreases at higher SiO₂ content range regardless of the surface modifications of SiO₂. It was attributed to the confinement of matrix chain since the inter-particle distance of adjacent SiO₂ approaches to the end-to-end distance of matrix chain, which a large molecular motion is restricted. Moreover, the average size of SiO₂ aggregation in iPP matrix was successfully evaluated by analyzing the contents dependence of the growth rate, assuming that the inter-particle distance with zero growth rate coincided with end-to-end distance of matrix iPP chain.     

Effect of the Metal Phenylphosphonates on the Nonisothermal Crystallization and Performance of Isotactic Polypropylene

The use of metal phenylphosphonates as efficient nucleating agents (NAs) for isotactic polypropylene (iPP) is reported and a possible structural correlation to the nucleation efficiency is studied. First, three kinds of metal phenylphosphonates are synthesized via reflux method: Ca(C₆H₅PO₃)?2H₂O (CaPPA), Ca(C₆H₅PO₃H)₂ (CaPPA2), and Al(HO₃PC₆H₅)(O₃PC₆H₅)?H₂O (AlPPA2). Then, the nonisothermal crystallization behaviors, mechanical, and optical properties of iPP composites are investigated. Compared to CaPPA2 and AlPPA2, CaPPA exhibits more effective heterogeneous nucleation effect during iPP crystallization. Furthermore, the nucleation efficiency of CaPPA is similar to industrial standard NAs NA‐21 and NA‐11. With the addition of 0.1 wt % CaPPA, the crystallization temperature is enhanced and the parameter F(T) of Mo method is decreased appreciably. Moreover, the flexural modulus, impact strength, and haze values of iPP composites are improved remarkably by introducing CaPPA. The CH/π interaction between polymer and aromatic cleft of CaPPA is considered to facilitate the attachment of iPP chains and subsequent nucleation and crystallization, which is verified by the viscoelastic properties of pure iPP and composites. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 161–173     

Study of thermo-oxidative chemical pre-treatment of isotactic polypropylene

A thermo-oxidative pre-treatment with chemical solutions is required in order to provide the adherence of inorganic semiconductor to the isotactic polypropylene (iPP) surface. A few thin films of iPP were treated with oxidizing solution at 90 °C. The crystalline properties were analyzed using XRD, and it had shown the presence of the α-monoclinic phases. The ATR-FTIR spectra had indicated that characteristic iPP peaks after thermo-oxidative chemical pre-treatment diminished sharply. Moreover, the new carbonyl groups (C = O) were observed, which signified oxidation. The UV–Vis spectra had showed a blue shift in the absorption edge, which corresponded to decrease in the optical band gap. The non-isothermal decomposition and crystallization kinetics of iPP films were studied and compared by means of thermogravimetric analysis and differential scanning calorimetric measurement. The values of the melting temperature T _m and the crystallization temperature T _c were found to be iPP surface structure and heating/cooling rate dependent. The activation energy of crystallization E _c was determined.     

Surface crystallization of polypropylene

Crystallization of compression-molded isotactic polypropylene and polyethylene is invariably spherulitic; generally, nucleation occurs randomly throughout the sample. In a special case where nucleation predominates at the surface, spherulitic growth centers become crowded and are forced to propagate unidirectionally into the bulk (transcrystallinity). Conditions for the formation of transcrystallinity have been investigated by optical and scanning electron microscopy. The occurrence of transcrystallinity is attributed to heterogeneous nucleation induced at the mold surface. To be effective, the mold surface must have a nucleating efficiency equal to or greater than that of adventitious nuclei present in the polymer. As the crystallization temperature approaches the melting point, the activity of mold surfaces is found to increase leading invariably to transcrystalline formation. The degree of activity of various mold surfaces correlates with the known activity of specific dispersed nucleating agents having similar chemical structures. Contrary to claims in the literature, the surface energy of the mold surface and temperature gradients across the melt surface do not play a primary role in transcrystalline formation of polypropylene.     

DSC and morphological studies on the crystallization behavior of β-nucleated isotactic polypropylene composites filled with Kevlar fibers

The crystallization behavior of β-nucleated isotactic polypropylene (PP) composites filled with Kevlar fibers (KFs), as well as that of non-nucleated PP/KF composites for comparison, was investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The morphological observations revealed that the KF addition could induce thick α-transcrystalline layer around their surfaces in PP/KF composites, while no obvious transcrystalline layer could be detected in β-nucleated PP/KF composites. Detailed DSC investigations suggested that for the PP/KF composites, the dominant modification was α-form, and the crystallization process of matrix was promoted by KF addition, as illustrated by faster isothermal crystallization rate, shorter induction time, and higher crystallization temperature. However, for β-nucleated PP/KF composites, the main modification was β-form, and their crystallization characteristics were independent of KF addition, indicating that the α-nucleating effect of KFs was absent in this system. The DSC results were confirmed by further rheological and wide angle X-ray diffraction (WAXD) studies. The mechanism of the formation of transcrystalline layer was also discussed.     

CO2‐delayed crystallization of isotactic polypropylene: A kinetic study

The effect of CO₂ on the nonisothermal crystallization of isotactic polypropylene (iPP) was studied with high‐pressure differential scanning calorimetry at cooling rates of 0.2–5 °C/min. CO₂ significantly delayed the melt crystallization of iPP, and both the crystallization temperature and the heat of crystallization decreased with increasing CO₂ pressure. The crystallization rate of iPP, as characterized by the half‐time, was also prolonged by the presence of CO₂. With a modified Ozawa model developed by Seo, the Avrami crystallization exponent n of iPP was calculated. This value was depressed by the addition of CO₂ and was strongly dependent on the CO₂ pressure at low cooling rates. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1518–1525, 2003     

Influence of CaCO<Subscript>3</Subscript> nanoparticles shape on thermal and crystallization behavior of isotactic polypropylene based nanocomposites

Summary The influence of calcium carbonate nanoparticles with different shapes (spherical and elongated) on the thermal properties and crystallization behavior of isotactic polypropylene was investigated. CaCO₃ nanoparticles were covered by an appropriate coating agent to improve the interfacial adhesion between the filler and the polyolefin matrix. The nanocomposites were prepared by melt mixing and subsequent compression molding. A remarkable effect of CaCO₃ on the thermal properties of iPP was observed. Moreover, the analysis of crystallization kinetics showed that CaCO₃ nanopowder coated with PP-MA are efficient nucleating agents for iPP, and the overall crystallization rate results higher than plain iPP.     

Transcrystallization of PTFE fiber/PP composites (I) crystallization kinetics and morphology

Transcrystallization of polypropylene (PP) on the polytetrafluoroethylene (PTFE) fiber was investigated. Both nucleation rate and crystal growth rate were determined by a polarized optical microscope. Based on the theory of heterogeneous nucleation, it has been found that the induction time can correlate well with the nucleation rate in determining the interfacial free energy difference function Δσ. The ratio of Δσ in the bulk matrix to that at the interface is 1.63 which implies the transcrystalline growth is favorable from a thermodynamic point of view. No difference in crystal growth rate of PP has been found in either spherulites or transcrystalline layers. On the basis of regime theory, a transition between regimes II and III was observed at ΔT = 48K. From the morphology studies, it has been found that the thickness of the transcrystalline layer increases with crystallization temperature, from 30 to 120 μm in the temperature range of 110–140°C. The growth of transcrystalline layer is hindered by the spherulites nucleated in the bulk. Moreover, the radius of spherulites adjacent to the transcrystalline layer is much smaller than that distant to the fiber. No significant increase in nucleation density at fiber ends is observed. Effect of internal stresses of fibers on the fiber's nucleating ability is not pronounced. © 1996 John Wiley & Sons, Inc.