The effect of sulfonation treatment on the structure and properties of isotactic polypropylene fibers prior to the carbonization stage

The effect of sulfonation treatment was investigated on the molecular structure and mechanical properties of isotactic polypropylene fibers extruded at a take up speed of 2500 m/min. It was found that at extensive sulfonation times, the sulfonated structure showed the characteristic features of carbonized structure as indicated by the results of the density and the X‐ray diffraction measurements. Mechanical properties of the sulfonated samples were found to be adversely affected by the sulfonation conditions. Scanning electron microscopy observations showed surface irregularities at low sulfonation times and fiber fractures at high sulfonation times. Polarized infrared spectroscopy measurements analysed by curve fitting procedure showed increasing molecular orientation of long helical chain segments represented by the IR band at 841 cm^?1 whereas amorphous structure represented by the IR band at 2723 cm^?1 showed gradual loss of orientation with the progress of sulfonation. IR bands assigned to the sulfonic acid groups formed during sulfonation treatment showed perpendicular polarization and low molecular orientation characteristics indicating the initiation and the development of crosslinking process being perpendicular to the fiber axis direction. Analysis of the equatorial X‐ray diffraction traces showed the loss of crystallinity where the paracrystalline phase disappeared faster than the crystalline α‐monoclinic phase. During the sulfonation treatment, content of amorphous phase showed gradual increase in line with decreasing crystallinity. In accordance with the loss of crystallinity, apparent crystallite sizes corresponding to the 110, 040 and 130 planes of the α‐monoclinic phase also decreased gradually with increasing sulfonation time. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The influence of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers

An investigation was carried out on the effects of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers annealed in an air heated environment at temperatures ranging from 60 to 140°C. Analysis of the equatorial X‐ray diffraction traces showed the presence of a three phase system of amorphous‐smectic‐monoclinic forms and revealed the transformation of the metastable smectic form to the highly stable monoclinic form as the annealing temperature is increased, resulting in an enhanced degree of crystallinity and the crystallite size. The improvements in the degree of crystallinity and the crystallite size became more remarkable above 120°C. Evaluation of the crystallinity was carried out using an analysis of density, infrared spectroscopy, and X‐ray diffraction methods whereas the state of the molecular orientation was evaluated using polarized infrared spectroscopy measurements only. Polarized infra‐red spectroscopy measurements after the curve fitting procedure showed a slight increase of the molecular orientation of the helical chain segments present in the crystalline phase represented by the IR bands at 841 and 998 cm^?1 whereas the amorphous structure represented by the IR band at 974 cm^?1 showed no significant change with increasing annealing temperature. The improvement in the molecular orientation of the crystalline phase became more remarkable above 120°C. Tensile strength of the annealed fibers increased with increasing annealing temperature but the elongation at break and the initial modulus were not affected as much as the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

The role of dry and wet isothermal annealing treatment on the structure and the mechanical properties of isotactic polypropylene fibers

Dry and wet annealing of isotactic polypropylene fibers was carried out under constant length at 120°C in air and in glycerine environments with annealing times ranging from 1 to 30 h. A detailed analysis of the infrared spectrum of samples annealed, especially in air, showed clear evidence of the surface oxidation as indicated by the appearance of oxygen containing functional groups. Annealing was found to lead to an improved structural organization as indicated by the crystallinity, crystallite size, and orientation measurements using X‐ray diffraction and infrared spectroscopy methods. Analysis of the X‐ray diffraction measurements showed a gradual transformation of metastable smectic phase to a more stable α‐monoclinic phase with increasing annealing time. Crystallinity, crystallite size, and orientation measurements performed for the samples annealed in air and in glycerine environments showed no distinct difference. Mechanical properties of the annealed samples were influenced by the annealing environment. Annealing in an air environment resulted in a continuous loss of tensile strength up to the annealing time of 12 h due to an oxidation related chain scission mechanism. On the other hand, annealing in glycerine environment resulted in a continuous and gradual increase of tensile strength without loss of physical form up to the annealing time of 30 h. It is suggested that wet annealing in glycerine environment should be used to obtain improved tensile strength values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical properties and superstructure of isotactic polypropylene fibers prepared by continuous vibrating zone‐drawing

A continuous vibrating zone‐drawing (CVZD) was applied to study the effect of vibration on the mechanical properties and superstructure of isotactic polypropylene fibers. The CVZD treatment was a new drawing method by which the fiber was continuously drawn at a rate of 0.5 m/min under vibration using the specially designed apparatus. The CVZD treatment was carried out in five steps at a drawing temperature of 150°C and a frequency of 100 Hz, and applied tensions increased step by step with processing in the range of 14.8 to 207 MPa. The obtained fiber had a birefringence of 0.0373, crystallinity of 62.4%, tensile modulus of 17.6 GPa, and tensile strength of 1.11 GPa. These values are higher than those of the continuous zone‐drawn isotactic polypropylene fiber previous reported. The vibration added to the fibers during the zone‐drawing was effective in developing amorphous orientation and improving the mechanical properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 600–608, 2001     

Formation and behaviour of low‐temperature melting peak of quenched and annealed isotactic polypropylene

The process of low‐melting point (LMP) α‐phase formation in a quenched and annealed isotactic polypropylene (iPP) was studied by means of differential scanning calorimetry. The influence of preparation conditions (quenching and annealing temperatures, annealing times and sample thickness), together with the measurement parameters (heating and cooling rates), on the iPP melting behaviour are analysed. The results reveal a constant yield of LMP crystals over a wide range of quenching temperatures. This study also suggests that the LMP α‐crystals originate from the crystallization of polymer portions, which are somewhere between the amorphous and the smectic phase on the macromolecular scale of order. © 2001 Society of Chemical Industry     

Further study on double‐melting endotherms of isotactic polypropylene

The origins of the single‐ and double‐melting endotherms of isotactic polypropylene crystallized at different temperatures were studied carefully by differential scanning calorimetry, wide‐angle X‐ray diffraction, and small‐angle X‐ray scattering. The experimental data show that spontaneous crystallization occurs when the crystallization temperature is lower than 117°C; thus the lamellae formed are imperfect. At a lower heating rate, the recrystallization or reorganization of these imperfect lamellae leads to double endotherms. On the other hand, when the crystallization temperature is higher than 136°C, two major kinds of lamellae with different thickness are developed during the isothermal process, which also results in the double‐melting endotherms. In the intermediate temperature range the lamellae formed are perfect, and there is only a single peak in the distribution of lamellar thickness. This explains the origin of the single‐melting endotherm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 163–170, 2000     

Nodular structure of isotactic polypropylene crystallizes from the melt

This article highlights the melt crystallization behavior of different grades of isotactic polypropylene (iPP) using a hot‐stage polarizing optical microscopy. iPP samples were heated up at a heating rate of 10°C/min passing the melting temperature and then kept for 3 min at a temperature range of 175–200°C before they cooled rapidly at 40°C/min to crystallize isothermally at a range of 130–145°C. It has been found that the temperature at which the samples were kept has a strong effect on the crystallization mode; for samples heated up and kept at temperatures below 190°C, the crystallization started with thin and long rods or nodules, which grew in the circumferential direction only while their lengths remain unchanged as the time passed. The shape of the nodules can be straight, circular, branched, or entangled, and they can grow parallel to each other or they can be crossed or in a random way. This phenomenon disappeared completely for samples melted and kept at temperatures above 195°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Orientated crystallization in discontinuous aramid fiber/isotactic polypropylene composites under shear flow conditions

Melt blends of short aramid fibers (AF) and isotactic polypropylene (iPP) are subjected to shear at 145°C and the structural evolution and final morphology are examined by in situ synchrotron X‐ray scattering/diffraction and high‐resolution scanning electron microscopy, respectively. The results indicate that the presence of short AFs significantly enhances the crystallization of iPP. It is argued that shear flow in this system exerts a twofold orientating action, namely, on the bulk iPP molecules and on the short AFs. The resultant crystalline morphology reflects the combined effects of crystallization on orientated iPP molecules to facilitate a shish kebab morphology and at the interface of the aligned fibers, to form transcrystallinity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1113–1118, 2005     

Influence of regioirregular structural units on the crystallization of isotactic polypropylene

Seven samples of isotactic polypropylene were examined to study the influence on the formation of the γ crystalline phase of possible regiodefects along the chain. Wide‐angle X‐ray diffraction allowed the determination of the percentage of the γ phase in the samples and ¹³C‐NMR spectroscopy was used to correlate the development of the γ phase with the existence of regioirregular structural units along the chain. Furthermore, it was possible to appraise the contributions given by the different families of lamellae to the small‐angle X‐ray diffraction patterns. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 375–384, 2001     

SAXS study applied to reversibly crosslinked isotactic polypropylene/clay nanocomposites

A new route based on reversibly crosslinking reactive extrusion is applied for the development of iPP/clay nanocomposites. Analysis of small‐angle X‐ray scattering (SAXS) reflections of isotactic polypropylene (iPP)/clay nanocomposites, prepared by two different mixing and chemical crosslinking methods (i.e., conventional and in situ), is presented and results are compared with preceding wide‐angle X‐ray diffraction (WAXD) results. It is shown that the presence of clay significantly affects the value of long spacing in iPP, as well as the coherence length of lamellar stacks. Results show that the size of the coherently diffracting nanodomains decreases in two stages, first rapidly and then slowly as a function of increasing clay content. This can be attributed to the influence of confined iPP lamellae under the effect of rising number of clay particles. The appearance of the γ‐crystalline form in the crosslinked iPP/clay nanocomposites is related with the difficulty in chain folding of iPP chains introduced by the chemical crosslinking process, as well as by the presence of clay particles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyolefins containing 1,3‐disubstituted cyclopentane units as nucleating agents for isotactic polypropylene

Polyolefins containing 1,3‐disubstituted cyclopentane units in the main chain have been synthesized by 1,3‐polymerization of cyclopentene (PCP), cyclization polymerization of 1,5‐hexadiene (PHD), and ring‐opening metathesis polymerization of norbornene following hydrogenation of the unsaturated main chain (H‐PNB) with various transition metal catalysts. These polyolefins were applied to nucleating agents for isotactic polypropylene, and relationship between the structure of the polyolefins and nucleating effect was studied by DSC, polarized optical microscope, and WAXD. All the polyolefins had an effect of nucleation for isotactic polypropylene (PP). Of the polymeric nucleating agents, H‐PNB showed the most effective nucleation. Addition of PCP, which was obtained with a nickel catalyst with diimine ligand, to PP induced β‐modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2953–2958, 2006     

Structure and morphology development during deformation of propylene based ethylene-propylene copolymer and its blends with isotactic polypropylene

The structure and morphology development during the deformation of metallocene based ethylene-propylene copolymers with dominant propylene moiety (C3 M-EP) and its isotactic polypropylene (M-iPP) blends were investigated by simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) using synchrotron radiation, high temperature tensile testing and differential scanning calorimetry (DSC). X-ray results showed that the structure and morphology in the blends of M-iPP/C3 M-EP are dictated by the M-iPP component. During stretching at room temperatures, both pure M-iPP and polymer blends exhibited the same transition from the α-form crystal to the mesophase. However, the α-form was found to be unchanged during the deformation of C3 M-EP copolymer, which indicated that the effect of local stress on the crystal domain in pure copolymer was too small to induce the phase transition. Although the DSC results showed that the blends in their isotropic state were immiscible with each other, the mechanical properties of the blends at high temperature (70 °C) indicated that they follow the conventional rule of mixing.     

A novel β‐nucleating agent for isotactic polypropylene

The nucleating ability of p‐cyclohexylamide carboxybenzene (β‐NA) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry, X‐ray diffraction, polarized optical microscopy and scanning electron microscopy. β‐NA is identified to have dual nucleating ability for α‐iPP and β‐iPP under appropriate kinetic conditions. The formation of β‐iPP is dependent on the content of β‐NA. The content of β‐phase can reach as high as 96.96% with the addition of only 0.05 wt% β‐NA. Under non‐isothermal crystallization the content of β‐iPP increases with increasing cooling rate. The maximum β‐crystal content is obtained at a cooling rate of 40 °C min^–1. The supermolecular structure of the β‐iPP is identified as a leaf‐like transcrystalline structure with an ordered lamellae arrangement perpendicular to the special surface of β‐NA. Under isothermal crystallization β‐crystals can be formed in the temperature range 80–140 °C. The content of β‐crystals reaches its maximum value at a crystallization temperature of 130 °C. © 2012 Society of Chemical Industry     

Effect of cavitation on the plastic deformation and failure of isotactic polypropylene

To clarify the effect of cavitation, which is mostly induced by crystalline phase, on the plastic deformation and failure of isotactic polypropylene, solid‐state annealing at 160°C for 1.5 h is adopted to change the crystalline phase only while the amorphous phase keeps nearly intact. With aid of a special video setup, the relation of true stress and strain as well as the evolution of volume strain with axial strain has been derived. Enhancing crystalline phase due to annealing increases the yield stress and volume strain simultaneously. Moreover, the strain corresponding to steep increasing of volume strain is comparable with that related to yield, indicating that cavitation at early stage is accompanied with process of yield. With knowledge of toughness derived from impact tensile stretching and essential work of fracture (EWF), respectively, the relationship between cavitation and toughness has been correlated to some degree. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The effect of talc on the crystallization of isotactic polypropylene

Isotactic polypropylene (iPP) has been crystallized in the presence of talc under the quiescent state and shear flow of injection molding. The resulting morphology has been investigated by means of polarizing microscopy, transmission electron microscopy, and wide angle X‐ray diffraction. In the quiescent state, the iPP lamellae grew from the surface of talc and the transcrystalline region was formed at the interface between iPP melt and the talc. The nucleation of iPP was very frequent on the cleavage plane of talc. The X‐ray diffraction pattern of the transcrystal showed a*‐axis orientation to the crystal growing direction. In injection‐molded samples of the talc‐filled iPP, the morphology of lamella growing from talc appeared as same as that of the transcrystal. However, the crystalline orientation of injection‐molded talc‐filled iPP, in which the b axis was oriented to the thickness direction and the a* and the c axis was oriented to the flow direction, was quite different from that of the transcrystal. This b‐axis orientation results from the orientation of the plate plane of talc, which induces the nucleation and the crystallization under shear flow. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1693–1703, 2001     

NMR,differential scanning calorimetry,and Fourier transform infrared characterization of the crystalline degree and crystallite dimensions of ethylene runs in isotactic polypropylene/ethylene–propylene copolymer blends (iPP/EP)

High‐resolution solid‐state ¹³C‐NMR, differential scanning calorimetry, and Fourier transform infrared spectroscopy were used to compare the very low crystalline degree and crystallite dimensions of ethylene runs in a series of isotactic polypropylene/ethylene–propylene copolymer blends exhibiting a range of properties. Results obtained from the three techniques on samples with the same thermal history are in a satisfying qualitative agreement. They show that the morphology of the polyethylene domains is only very slightly dependent on the viscosity ratio of the two blend components. On the opposite, it is largely governed by the ethylene content of the ethylene–propylene copolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3165–3172, 1999     

Influence of thermal treatments,molecular weight,and molecular weight distribution on the crystallization of β‐isotactic polypropylene

Six samples of isotactic polypropylene were examined to study the influence of the thermal treatments and the molecular weights and their distribution on the β‐crystallization of the polymer. The highest amount of the β‐phase was obtained by isothermal crystallization and in correspondence of high average molecular weights and wide molecular weight distributions. Small‐angle X‐ray scattering pointed out that a partial β‐crystallization seems not to influence the lamellar morphology parameters. Differential scanning calorimetry measurements, at different heating rates, allowed us to confirm that the multiple melting endotherms behavior of the β‐phase is to be correlated to a melting–recrystallization–melting mechanism. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1008–1012, 2004     

On the overdrawing of melt‐spun isotactic polypropylene tapes

The morphology and mechanical properties of melt‐spun and post‐drawn isotactic polypropylene (iPP) tapes have been studied in order to examine their dependence on the post‐draw ratio applied. Special attention is focused on the characterization of the so‐called overdrawing behavior of the tapes; at a certain draw ratio, a change of the optical appearance of the tape from transparent to opaque is observed. Overdrawing is accompanied with changes in the mechanical properties, surface, and morphology of the tapes. For post‐draw ratios without overdrawing, and for highly overdrawn tapes, the variation in the mechanical properties measured is very small, but for slightly overdrawn tapes, a large scattering of mechanical properties has been measured. In the latter case, this behavior is related to the start of internal delamination of the tapes during post drawing. It is shown that strongly overdrawn tapes have excellent mechanical properties, in particular, high specific stiffness and strength. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2920–2931, 2007     

Investigation of the stereodefect distribution and conformational behavior of isotactic polypropylene polymerized with different Ziegler–Natta catalysts

Two isotactic polypropylene (iPP) samples (PP-A and PP-B) were obtained by utilizing two different heterogeneous Ziegler–Natta catalysts in a given polymerization system. The molecular structure and conformational behavior of the samples were studied. The results of determination of xylene soluble material (XS) and ¹³C NMR showed that the average isotacticity of the samples were nearly same. However, the results of high-resolution high-temperature ¹³C NMR (HRHT ¹³C NMR) and successive self-nucleation and annealing (SSA) fractionation revealed that the amount of high isotacticity of PP-B was lower than that of PP-A, and the amount of relative medium and low isotacticity of PP-B was higher than PP-A, indicating that the stereodefect distribution of PP-B was more uniform than PP-A. The calculation of average meso sequence length from SSA was found to be in good agreement with that calculated from the results of HRHT ¹³C NMR. Moreover, Fourier transformation infrared was utilized to study the influence of stereodefect distribution on the conformational behavior of iPP. The result suggested that the molecular conformation of the PP-B was more disordered than PP-A, the regularity of molecular structure for PP-B was lower than that of PP-A. The related action mechanism and the influences of which on crystallization behavior were discussed. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Formation of microporous membrane of isotactic polypropylene in dibutyl phthalate‐soybean oil via thermally induced phase separation

Isotactic polypropylene (iPP) microporous membranes were prepared via the thermally induced phase separation (TIPS) process with the diluents being dibutyl phthalate (DBP) and soybean oil mixture. By changing the weight ratio of DBP to soybean oil systematically, it was determined experimentally that the cloud‐point curves were influenced to a great extent, while the crystallization curves showed much less dependence on the diluents composition. Scanning electron microscopy (SEM) showed that the resulting membrane morphologies changed significantly by varying the composition of the diluents, i.e., by changing the interaction parameter and other characteristics of diluents, the interwoven or celluar structure can be fabricated successfully at a fixed polymer concentration under the same cooling conditions. Different growth rates of iPP spherulite were obtained in the diluents with different composition. It is shown that the spherulites growth rates may be also attributed to the great variations of the final microporous morphology to a certain extent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007