Orientation of HDPE inclusions within solid‐state drawn rubber‐modified isotactic polypropylene: DSC insight

Effect of drawing temperature on the melting behavior of oriented isotactic polypropylene (PP) modified with ethylene‐propylene‐diene monomer rubber with a small amount of high‐density polyethylene (HDPE) is explored in this study. Injection‐molded specimens both neat and 8 vol % modified PP were solid‐state drawn to natural drawing ratio and characterized by X‐ray diffraction, dynamic mechanical analysis (DMA), Charpy impact test and differential scanning calorimetry (DSC). A synergy of orientation and embedding rubber particles caused a significant increase of low‐temperature notched impact strength of oriented blends. It was shown, that the DSC method can be used successfully for the indirect but very sensitive characterization of orientation on a nanometre scale. At the drawing temperature of 120°C, the DSC data indicated an incomplete transition of the PP crystalline structure: This is reflected by splitting and shifting of the melting peak of PP. An increase of the melting temperature of the HDPE inclusions by 3.5°C reflects the high orientation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Controlling of threadline dynamics via a novel method to develop ultra‐high performance polypropylene filaments

A detailed study was conducted to investigate the effects of horizontal isothermal bath (hIB) on the production of ultra‐high performance polypropylene filaments. Two different commercial PP polymers were used with the melt flow rate of 4.1 and 36 g/10 min. The optimum process conditions depended on polymer molecular weight. Fibers showed distinct precursor morphology for each at each optimum process condition. However, two sets of filaments demonstrated similar fiber tenacity and modulus of about 7 and 75 g d^?1, respectively, for as‐spun and more than 12 g d^?1 for tenacity and more than 190 g d^?1 for modulus values of drawn fibers after just 1.49 draw ratio. The mean value for the modulus after the drawing process for the high melt flow rate was 196 g d^?1. The theoretical modulus of PP is 35–42 GPa¹⁹, (275–330 g d^?1), shows the hIB fiber's modulus performance is approaching its theoretical maximum value. Fibers had greatly improved thermal properties, degree of crystallinity, crystalline and amorphous orientation factors. The hIB spinning system produced highly oriented and predominantly amorphous structure for as‐spun fibers and a well‐defined, highly oriented crystalline fibrillar and amorphous structure after drawing process with the draw ratios lower than 1.5. POLYM. ENG. SCI., 55:327–339, 2015. © 2014 Society of Plastics Engineers     

High modulus/tenacity filaments from blends of different molecular weights of polypropylene

Polypropylene (PP) filaments are prepared by blending two different molecular weight components of PP. A melt‐spinning process to produce filaments includes mixing of components, extrusion, and two‐stage drawing, followed by a unique Gradient Drawing? process. Blending results in highly deformable as‐spun filaments with high draw ratios. For 90:10 blends of PP samples with melt flow indexes of 35 and 3, a high level of crystallinity and crystalline and amorphous orientations are obtained. A sonic modulus of 28 GPa, dynamic modulus of 20 GPa, tensile modulus of 16 GPa, and tenacity of 667 MPa are achieved. These samples are dimensionally stable up to ～100°C. All steps in the production of the filaments are continuous. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1021–1028, 2005     

Preparation of poly(lactic acid) fiber by dry‐jet‐wet‐spinning. I. Influence of draw ratio on fiber properties

Poly(lactic acid) fiber was prepared by dry‐jet‐wet spinning of the polymer from chloroform solution and with methanol as the precipitating medium. The as‐spun fiber was subsequently made into high strength fiber by two‐step process of drawing at a temperature of 90°C and subsequent heat setting in the temperature range of 120°C. The draw ratio had significant influence on the crystallinity and the tensile strength of the fiber. The fiber with the tenacity of 0.6 GPa and modulus of 8.2 GPa was achieved at a draw ratio of 8. The differential scanning calorimetry revealed an increase in the glass‐transition temperature with the increase in the draw ratio, which suggests the orientation of chains during the drawing process. The surface morphology of the filament as revealed by scanning electron microscopy shows that fibers are porous in nature, but a significant reduction in the porosity and pore size of the fiber was observed with the increase in the draw ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1239–1246, 2006     

Melt spinning of poly(L‐lactic acid) and its biodegradability

The melt spinning and melt drawing of poly(L ‐lactic acid) (PLLA) were carried out with a melt‐spinning machine, and the mechanical properties, structure, and biodegradability of PLLA fiber were investigated. PLLA fiber with a tensile strength of 0.81 GPa was successfully obtained through two steps of drawing at a draw ratio of 18 in hot water. This fiber had enough tensile strength for common engineering use. The fiber could be degraded under controlled composting conditions at 70°C for 1 week. In scanning electron microscopy observations of the fiber, a regular pattern of cracks running along the vertical direction to the fiber axis was clearly observed. This suggested that the PLLA fiber built up a highly ordered structure arranged along the direction of the fiber axis. After the fiber was left to lie in the ground for 1 year, however, the surface of the fiber was still smooth, and the tensile strength did not decrease much. This PLLA fiber could not be hydrolyzed after 1 month of steeping in a buffer solution at 37°C, but it was rapidly hydrolyzed at more than 60°C. It was suggested that the degradation (hydrolysis) rate of PLLA depended on the glass‐transition temperature. Upon hydrolysis at 80°C for 48 h, a regular crack along the vertical direction to the fiber axis was found that was very similar to that observed in degradation under composting conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2118–2124, 2005     

Performance of long glass fiber‐reinforced polypropylene composites at different injection temperature

Long glass fiber‐reinforced polypropylene composites were prepared using self‐designed impregnation device. Effects of the different injection temperature on mechanical properties, crystallization, thermal, and dynamic mechanical properties of long glass fiber‐reinforced polypropylene composites were discussed. The differential scanning calorimetry (DSC) results indicate that the melting peak temperature of PP/LGF composites gradually reduced, however, the crystallinity of PP/LGF composites gradually increased with increasing injection temperature. Thermo‐gravimetric analyzer (TGA) results demonstrate that with increasing injection temperature, the temperature of the PP/LGF composites melt increased, the viscosity of the PP/LGF composites melt lowered, the mold filling of the PP/LGF composites melt was easy, the shear force of glass fiber was relatively low, which made the residual length of glass fiber in products increase. Dynamic thermal mechanical analyzer (DMA) results show that the storage modulus of PP/LGF composites is the highest while the injection temperature is at 290°C, and the peak value of tan σ of PP /LGF composites at 290°C is minimal, which indicates that the mechanical properties of PP /LGF composites at 290°C is the best. What' more, the injection temperature at 290°C significantly ameliorated “glass fiber rich skin” of products of glass fiber‐reinforced composites. J. VINYL ADDIT. TECHNOL., 24:233–238, 2018. © 2016 Society of Plastics Engineers     

Tailoring the crystalline structure of polypropylene parts molded through water‐assisted injection molding: Effects of melt temperature and polymeric nucleating agent

The melt temperature and a special polymeric nucleating agent [acrylonitrile–styrene copolymer (SAN)] were investigated to find an effective way for tailoring the crystalline structures of the water‐assisted injection‐molded polypropylene (WAIM PP) parts. The results showed that lowering the melt temperature led to the formation of a small amount of β‐form crystals in both outer and core layers of the WAIM PP parts. Nevertheless, the melt temperature had little effect on tailoring the crystalline structures of the WAIM PP parts. The addition of a low content (6 wt%) of the SAN was interestingly found to gradually influence the crystalline structures as lowering the melt temperature. WAIM PP/SAN blend parts with high contents of β‐form in both outer and core layers (30.7 and 18.4%, respectively), and high contents of transcrystals in the inner layer were molded at relatively low melt temperature (180°C), whereas the SAN had little influence on the crystalline structures at higher melt temperature (230°C). The formation of the transcrystals was ascribed to the in situ fibrillation of the SAN, which was resulted from high shear and cooling rates caused by high‐pressure water penetration during WAIM. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Thermal degradation of polypropylene in a capillary rheometer

Melt viscosity of a polypropylene (PP) resin was measured in a capillary rheometer between 220 and 260°C. The melt viscosity showed a power law behavior with strong shear rate dependence. The effects of temperature and shear rate on the degradation were studied in the rheometer by heating at 260 and 280°C, and extruding at shear rates up to 10000 sec ?1 . Melt flow index (MFI) of samples after shearing and heating treatment was measured to characterize the molecular weight change. An increase in MFI was found for PP sheared at high temperature. Heating for longer time also increased MFI. Increase of shear rate had a small effect on increasing MFI at 260°C but produced a larger effect at 280°C. A constant increment in MFI was observed in PP subjected to high temperature processing and was attributed to degradation due to oxygenated products.     

Structure evolution of melt‐spun poly(vinyl alcohol) fibers during hot‐drawing

The drawability of melt‐spun poly(vinyl alcohol) (PVA) fibers and its structure evolution during hot‐drawing process were studied by differential scanning calorimetry (DSC), two dimensional X‐ray diffraction (2‐D WAXD) and dynamic mechanical analysis (DMA). The results showed that the water content of PVA fibers should be controlled before hot‐drawing and the proper drying condition was drying at 200°C for 3 min. PVA fibers with excellent mechanical properties could be obtained by drawing at 200°C and 100 mm/min. The melt point and crystallinity of PVA fibers increased with the draw ratio increasing. The 2‐D WAXD patterns of PVA fibers changed from circular scattering pattern to sharp diffraction point, confirming the change of PVA fibers from random orientation to high degree orientation. Accordingly, the tensile strength of PVA fibers enhanced by hot‐drawing, reaching 1.85 GPa when the draw ratio was 16. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt flow indexer evidence of high‐temperature transitions in molten high‐density polyethylenes

A melt flow indexer (MFI) was used to investigate high‐temperature transitions in melts of high‐density polyethylene (HDPE). The MFI data were obtained in the range 190–230°C. These transitions were found in the MFI at about 210 and 225°C and reproduced in a Haake melt blender. Polystyrene was used in the blender experiment to demonstrate typical amorphous behavior. For HDPE melts, the MFI–temperature behavior and the torque–temperature data of the blender were found to be alternative images of the same anomalous temperature dependency in the range 210–225°C. Also, the Haake melt blender was able to reproduce the 150°C transition observed by Kolnaar and Keller in the extrusion of HDPE. Regardless of the simplicity of the MFI device, results are in agreement with our previous DSC findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1309–1313, 2004     

Numerical modeling,simulation, and experimental validation of predicting fiber diameter in wide‐slot positive‐pressure spunbonding process

An air‐drawing model of polypropylene (PP) polymer and an air jet flow field model in wide‐slot positive‐pressure spunbonding process are established. The influences of the density and the specific heat capacity of polymer melt at constant pressure changing with polymer temperature on the fiber diameter have been studied. The predicted fiber diameter agrees with the experimental data as well. The effects of the processing parameters on the fiber diameter have been investigated. The air jet flow field model is solved by means of the finite difference method. The numerical simulation computation results of distribution of the fiber diameter match quite well with the experimental data. The air‐drawing model of polymers is solved with the help of the distributions of the air velocity. It can be concluded that the higher air velocity and air temperature can yield the finer fibers diameter. The higher inlet pressure, longer drawing segment length, smaller air knife edge, longer exit length, smaller slot width, and smaller jet angle can all cause higher air velocity and air pressure along z‐axis position, which are beneficial to the air drawing of the polymer melt and thus to reduce the fiber diameter. The experimental results show that the agreement between the predicted results and the experimental measured data is very better, which verifies the reliability of these models. Also, they reveal great prospects for this work in the field of computer‐assisted design (CAD) of spunbonding process. POLYM. ENG. SCI., 58:1371–1380, 2018. © 2017 Society of Plastics Engineers     

Structure and isothermal crystallization behavior of polypropylene prepared at high polymerization temperature

The structure, morphology, and isothermal crystallization behaviors of polypropylene (PP) prepared with heterogeneous Ziegler‐Natta catalyst at high temperature (100°C) were investigated with differential scanning calorimetry, wide‐angle X‐ray diffraction, temperature‐rising elution fractionation, gel permeation chromatography, and ¹³C NMR. The results reveal that the crystalline structure changes with variation of the composition of the PP. The isotactic PP (iPP)1 prepared with Et₃Al and “TMA‐depleted” methylaluminoxane crystallizes from the melt in the mixtures of the α and β forms, whereas each fraction obtained from pure PP1 does not show β‐PP crystal at the same crystallization condition. In addition, the γ‐PP crystal is appeared for the fractions of low mmmm%‐[mmmm] (mmmm pentad content) values and molecular weight. Moreover, it was found that the iPP2 or iPP3 prepared with Hex₃Al crystallizes from the melt in mixtures of the α and γ forms, even at atmospheric pressure and for high molecular weight. The microstructure showed in the PP samples obtained at high temperature could be well explained with the shift in the alkylaluminium‐donor equilibrium reactions at high polymerization temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of melt‐processable polyimides derived from 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)benzene

A series of molecular‐weight‐controlled imide resins end‐capped with phenylethynyl groups were prepared through the polycondensation of a mixture of 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)benzene and 1,3‐bis(4‐aminophenoxy)benzene with 4,4′‐oxydiphthalic anhydride in the presence of 4‐phenylethynylphthalic anhydride as an end‐capping agent. The effects of the resin chemical structures and molecular weights on their melt processability and thermal properties were systematically investigated. The experimental results demonstrated that the molecular‐weight‐controlled imide resins exhibited not only meltability and melt stability but also low melt viscosity and high fluidability at temperatures lower than 280°C. The molecular‐weight‐controlled imide resins could be thermally cured at 371°C to yield thermoset polyimides by polymer chain extension and crosslinking. The neat thermoset polyimides showed excellent thermal stability, with an initial thermal decomposition temperature of more than 500°C and high glass‐transition temperatures greater than 290°C, and good mechanical properties, with flexural strengths in the range of 140.1–163.6 MPa, flexural moduli of 3.0–3.6 GPa, tensile strengths of 60.7–93.8 MPa, and elongations at break as high as 14.7%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Melt spinning of β‐phase poly(vinylidene fluoride) yarns with and without a conductive core

When poly(vinylidene fluoride) (PVDF) is to be used as a piezoelectric material, the processing must include the formation of polar β‐phase crystallites, as well as the application of electrically conducting charge collectors, that is, electrodes. In this article, results from the melt spinning of PVDF yarns and a novel bicomponent PVDF‐yarn with a conductive carbon black/polypropylene (CB/PP) core are presented. Melt spinning has been done under conditions typical for industrial large‐scale fiber production. The effects on the resulting crystalline structure of varying the spinning velocity, draw rate, and draw temperature are discussed. The results show that, for maximum α‐to‐β phase transformation, cold drawing should take place at a temperature between 70 and 90°C, and both the draw ratio and the draw rate should be as high as possible. It was observed that the cold drawing necessary to form β‐phase crystallinity simultaneously leads to a decrease in the core conductivity of the bicomponent yarns. In this work, the melt spinning of bicomponent fibers with high‐β‐phase PVDF in the sheath and a CB/PP core was successfully accomplished. The core material remained electrically conductive, paving the way for the use of a CB‐polymer compound as inner electrode in the melt spinning of piezoelectric bicomponent fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of polypropylene‐graft‐cardanol by reactive extrusion and its composite material with bamboo powder

The polypropylene‐graft‐cardanol was prepared by reactive extrusion, which is solvent‐free melt process, continuous processing, and controllable over residence time. The effect of monomer and initiator concentration on grafting ratio, grafting efficiency, and melt flow index (MFI) was also studied. The yield was quantified by UV–vis spectrometer. The chemical structure was investigated by infrared spectroscopy and gel ratio. A possible mechanism was supposed. The particular structure of cardanol can retain the MFI value of matrix resins and prevent polypropylene (PP) from being decomposed. The grafting ratio could be easily obtained from an experimental formula deduced from the linearity relationship between grafting ratio and MFI. The effect of cardanol grafted onto PP on the compatibility of PP and bamboo powder was studied by contact angle measurements, scanning electron microscopy, and tensile properties test. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An effective method of processing immiscible polymer blends into strong fiber

A unique methodology employing a “nearly co‐continuous morphology” for processing immiscible polymers into strong fiber is presented, and an immiscible polypropylene/polystyrene (PP/PS) blend is used as a model system to demonstrate the effectiveness of this methodology. The “nearly co‐continuous morphology” is easier to obtain than the fully co‐continuous structure, and yet, it provides an engineering solution to the production of strong fiber from an immiscible polymer blend. In addition, a process different from traditional melt spinning is used to prepare fiber with good mechanical properties. Traditional melt spinning involves large jet stretch and therefore introduces large interfacial orientation but little molecular orientation in polymer blends. To address this issue, the PP/PS blend is spun with nearly zero jet stretch and after solidification undergoes hot drawing at temperature close to the glass transition temperature of PS. This process sequence imparts a large degree of molecular orientation to the PP phase and produces a strong fiber. The proposed methodology can be extended to other blend systems and provides a potential route for directly recycling commingled polymer waste without preseparation or compatibilization. POLYM. ENG. SCI., 59:2052–2061, 2019. © 2019 Society of Plastics Engineers     

Recycled‐disposable‐chopstick‐fiber‐reinforced polypropylene green composites

The utilization of disposable chopsticks is very popular in Taiwan, China, and Japan and is one of the major sources of waste in these countries. In this study, recycled disposable chopstick fiber was chemically modified. Subsequently, this modified fiber and polypropylene‐graft‐maleic anhydride were added to polypropylene (PP) to form novel fiber‐reinforced green composites. A heat‐deflection temperature (HDT) test showed an increase of approximately 81% for PP with the addition of 60‐phr fibers, and the HDT of the composite could reach up to 144.8°C. In addition, the tensile strength, Young's modulus, and impact strength were 66, 160.3, and 97.1%, respectively, when the composite material was 40‐phr fibers. Furthermore, this type of reinforced PP would be more environmentally friendly than an artificial‐additive‐reinforced one. It could also effectively reduce and reuse the waste of disposable chopsticks and lower the costs of the materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. I. Temperature dependence

Polypropylene (PP)‐type resins with narrow molecular weight distribution, such as PP‐type thermoplastic elastomer PER and controlled‐rheology PP (CRPP) made by peroxide degradation of high molecular weight PP, have a problem of easy generation of skin roughness at extrusion. To examine the present state, the occurrence of skin roughness in PER and CRPP at extrusion was investigated with a capillary rheometer in a shear rate range of 12–6100 s^?1 and a temperature range of 180–280°C. A homo‐PP (HPP) and a block‐PP (BPP) with usual molecular weight distributions were used for comparison. HPP and BPP with usual molecular weight distributions show smooth extrudates at low shear rates and abruptly generate severe skin roughness “elastic failure” originating at the die entrance at a higher shear rate. PER and CRPP with narrow molecular weight distributions easily generate “sharkskin” melt fracture originating at the die exit, from a shear rate nearly one decade lower than rates of elastic failure of HPP and BPP. The sharkskin becomes more severe, with increasing shear rate, and attains to the elastic failure. The critical shear rate at which sharkskin occurs increases with increasing extrusion temperature. The critical shear rate is about 20 s^?1 at 180°C and about 120 s^?1 at 280°C, which is in the range encountered by the molten resin at extrusion processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2111–2119, 2002     

Structure and melt rheology of long‐chain branching polypropylene/clay nanocomposites

Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Melting and crystallization behaviors of injection‐molded polypropylene

The melting and crystallization behaviors of the skin layer in an injection‐molded isotactic polypropylene (PP) have been studied, mainly in comparison with those of the core layer and subsidiarily in comparison with those of a compression‐molded PP and a nucleator (talc)–added PP. The skin layer contains about 5% crystals, which have a high melting point of up to 184°C. They thermally vanish by melting once. The subsequent melting history will scarcely affect the melting behaviors. On the other hand, crystallization behaviors are strongly affected by the melting history. The skin layer crystallizes in a wide temperature range at high temperature. This tendency weakens with increasing melting temperature, approaching a constant and that of the core layer above 230°C, which suggests that the memory effect of the residual structure of PP vanishes by melting above 230°C. In explaining these experimental results, it is assumed that the residual structure substance is a melt orientation of molecular chains that works as crystallization nuclei and that the vanishing of the residual structure is nothing but a relaxation of the melt orientation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1751–1762, 2000