Effect of high‐energy ball milling on the structure and mechanical properties of ultra‐high molecular weight polyethylene

The structure and properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE) powder after severe deformation processing in a planetary ball mill were studied by means of scanning electron microscopy, differential scanning calorimetry, and X‐ray analysis. We found that the severe deformation processing of UHMWPE changed the morphology of the powder and caused amorphization and partial changes in the structure of the crystalline phase. Monolithic samples were obtained from the pretreated polymer with a hot‐pressing method in a wide range of temperatures. The effect of preliminary deformation processing on the mechanical properties of UHMWPE was studied. It was revealed that during monolitization in its melting temperature range, the mechanical properties of the powder increased, whereas the percentage elongation decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2971–2977, 2013     

Morphological and structural development of recycled crosslinked polyethylene during solid‐state mechanochemical milling

Waste crosslinked polyethylene (XLPE) was partially decrosslinked to obtain a thermoplastic recycled material through solid‐state mechanochemical milling with pan‐mill equipment at ambient temperature. The gel fraction and size exclusion chromatography measurements showed that the gel content of XLPE decreased remarkably with increasing cycles of mechanochemical milling, whereas the molecular weight of the sol fraction was not significantly reduced; this indicated the realization of partial decrosslinking during mechanochemical milling. Differential scanning calorimetry and X‐ray diffraction analysis showed that the melting temperature of decrosslinked polyethylene increased by 3.5°C because the bigger crystallites size resulting from the higher mobility of the chain segment. The improved thermoplastic characteristic of XLPE after mechanochemical milling were confirmed by scanning electron microscopy and rheological measurement. The mechanical properties of recycled XLPE also achieved significant improvement after mechanochemical milling. Solid‐state mechanochemical milling is a cost‐effective, reliable, and environmentally friendly method for recycling XLPE at ambient temperature without any additional materials or chemicals. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigation on dry spinning process of ultrahigh molecular weight polyethylene/decalin solution

The relationship between the draw‐down ratio in the dry spinning process of ultrahigh molecular weight polyethylene/decalin solution and the fiber performance through maximized after‐drawing was investigated. The structural development during the after‐drawing process was analyzed by scanning electron microscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, sonic velocity, and FTIR measurements. An optimum draw‐down ratio was found in the multihole dry spinning process, which may be explained by molecular disentanglement and the composite effect of entropy and the viscosity component. The as‐spun fiber by draw‐down had an obvious shish kebab morphology, lower crystallinity, and a higher melting temperature compared with a free extrusion sample, and higher crystallinity and melting temperature compared with the fiber by first‐stage after‐drawing. During the subsequent after‐drawing process, the crystallinity, melting temperature, X‐ray diffraction, and sonic velocity orientation factors increased slowly in the higher after‐drawing ratio region, which was not consistent with the rising tendency of the tensile properties. The polarized and unpolarized IR spectra reflected the variations of the orientation and the content of the folded chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 474–483, 2005     

Effects of a mixture of stabilizers on the structure and mechanical properties of polyethylene during reprocessing

The properties of two polyethylenes [a high‐density polyethylene (HDPE) and a low‐density polyethylene (LDPE)] were studied after several extrusion cycles. To reduce the degradation effects during the reprocessing, a mixture of two stabilizers was added to the formulations. The predominant degradation mechanism was chain scission for the HDPE and chain branching and crosslinking for the LDPE. For both polyethylenes the FTIR spectra exhibited a growth in the number of carbonyl groups as a function of the number of extrusion cycles. Their tensile properties were degraded with the reprocessing but both polyethylenes maintained their nearly constant thermal behavior and crystallinity. The addition of a primary phenolic antioxidant and a secondary phosphite antioxidant preserved the melt behavior of virgin materials after the reprocessing and reduced the degradation effects. From the tensile tests, the efficiency of the antioxidants in the LDPE was very high and, after the reprocessing, the material retained the mechanical properties of virgin LDPE. The efficiency of the antioxidants for the HDPE was not significant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3910–3916, 2004     

Experimental approach to mechanical property variability through a high‐density polyethylene gas pipe wall

An experimental investigation was designed to establish the distribution of mechanical properties throughout a high‐density polyethylene (HDPE) gas pipe wall. The proposed approach used a continuous and uniform filament that was automatically machined from the pipe on a precision lathe at a very low cutting speed and an optimal depth of cut to minimize heating and structural disturbances. Typical engineering stress–strain curves, in every layer, were obtained on a testing machine especially designed for polymers, and they were statistically analyzed. The stress–strain behavior of HDPE pipe material could basically be divided into three distinctive zones, the second of which remained important. The average stress level illustrating cold drawing for a given layer was almost constant throughout the pipe wall. The measured stresses and moduli correlated very well with the pipe thickness, and they increased from the outer layers toward the inner layers. This was explained by the crystallinity evolution because the pipe production process was based on a convective water‐cooling system with a temperature gradient, which generated residual stresses. Computed statistical stress–strain correlations at yielding, the onset of cold drawing, and fracture points revealed acceptable linear relations for an error level of p ≤ 0.05. On the other hand, an increasing linear correlation characterized the relationship of the yield stress and elastic modulus. This result was confirmed by literature for standard specimens, prepared by compression molding, that did not represent an actual pipe structure with respect to an extrusion thermomechanical history. Such an approach to mechanical property variability within an HDPE pipe wall highlighted the complexity of the hierarchical structure behavior in terms of stress–strain and long‐term brittle failure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 272–281, 2005     

Phase structural analyses of polyethylene extrusion coatings on high‐density papers. II. Influence of paper surface properties on the polyethylene morphology

Paper samples of three different qualities were extrusion coated with low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE). The morphological phases of the polyethylene layers have been quantified by ¹³C solid‐state high‐resolution NMR. Shear forces in the process initiate the formation of the monoclinic crystallites. The surface tensions of the high‐density papers have influence on the degree of interaction between the two materials and how these shear forces work. The paper surface properties will thus have an influence on properties and the size of the monoclinic crystalline mass fraction of the polyethylene coating. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 226–234, 2004     

Effect of the matrix resin structure on the mechanical properties and braking performance of organic brake pads

Two chemically modified phenolic resins (PFs) designed and developed for the matrix resins of organic friction materials were characterized. The braking performance of organic brake pads based on the two modified resins and reinforced with hybrid fibers was investigated on a full‐scale test bench. The results indicate that the modified PF with more internal friction units possessed much higher impact and compression strengths, greater toughness, and better braking stability. We concluded that the matrix resin with more adjustable structural units allowed for an adjustable Young's modulus and dynamic mechanical properties and, hence, could indirectly allow an adjustable friction coefficient for organic brake pads during braking process and, furthermore, enable the optimization of braking stability of the friction couples. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

Effect of solid‐state shear milling on structure and properties of HDPE/UHMWPE blends

The structure and properties of HDPE/UHMWPE blends prepared through a pan‐milling reactor in solid state at ambient temperature were compared with the blends made by melt mixing. The changes of structure and properties of the blends were investigated by FTIR, melt flow index, mechanical properties, dynamic rheological measurement, DSC, and WAXD. DSC measurement illustrated that after pan‐milling treatment, the half‐width of the melting temperature became smaller. The more content of UHMWPE added in the blend, the more evident change was observed. Combined with the dynamic rheological analysis, it was proved that, the pan‐milling treatment can improve the compatibility of the HDPE/UHMWPE blends. X‐ray diffraction analysis showed that after pan‐milling treatment some ordered structure could be induced, but after heat treatment, the induced crystalline structure disappeared. The tensile properties of pan‐milled HDPE/UHMWPE blends also achieved improvement after pan milling treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39916.     

Nanoparticle effects on structure and properties of polypropylene meltblown webs

The effect of nanoclay additive on the structure, morphology, and mechanical properties of polypropylene meltblown webs is reported here for the first time. Effect of nanoclay on the meltblown processing, resultant fiber web structure, and properties are discussed. Combination of wide‐angle x‐ray diffraction, differential scanning calorimetry, and transmission electron microscopy were used to determine the nature of clay dispersion in the polypropylene fiber matrix and resultant morphology. Transmission electron microscopy micrographs revealed nanolevel dispersion of the additive in the fiber web. Clay additive did not offer any benefit as far as the mechanical properties of the meltblown web are concerned. Meltblown web samples with nanoclay had higher variability in web structure, high air permeability, high stiffness, and lower mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure and properties of ultraviolet‐irradiated high density polyethylene at different environmental temperatures

C? O, C?O, and C(?O)O oxygen‐containing groups were introduced onto the molecular chain of high‐density polyethylene (HDPE) through ultraviolet irradiation in air. The introduction rate of the oxygen‐containing groups onto HDPE increased with increasing environmental temperature. After ultraviolet irradiation, the molecular weight of HDPE decreased, and its distribution became wider; the melting temperature, contact angle with water, and impact strength decreased; the degree of crystallinity and yield strength increased; and their variation amplitude increased with environmental temperature. The environmental temperature had an effect on the gel content of irradiated HDPE. HDPE‐irradiated for 48 h at 35° and 50°C were not crosslinked. However, gelation took place in HDPE irradiated for 24 h at 70°C. HDPE irradiated at a high environmental temperature was more effective than that irradiated at a low environmental temperature in compatibilizing HDPE with PVA. Compared with the 83/17 HDPE/PVA blend, the yield and notched impact strength of the 73/17 HDPE/PVA blend compatibilized with 10% HDPE irradiated for 24 h at an environmental temperature of 70°C increased from 30.8 MPa and 110 J/m to 34.9 MPa and 142 J/m, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2966–2969, 2003     

Biaxial orientation behavior of polystyrene: Orientation and properties

Square sheets of extrusion grade polystyrene (PS) were biaxially stretched using a laboratory biaxial stretcher. The effects of process parameters such as stretch ratio, drawing sequence, drawing speed, and temperature were studied. Birefringence, mechanical properties, and thermal shrinkage of the stretched sheets were the focus of this study. A high orientation was achieved at high stretch ratio, and orientations from uniaxial to equi‐biaxial were obtained by controlling the relative magnitude of stretch ratio in machine (MD) and transverse (TD) directions. Stretching increased tensile strength and elongation at break significantly, which indicated an improvement in the toughness of the oriented PS sheets. Those properties were correlated with biaxial orientation factors: a rapid increase was observed for both tensile strength and elongation at break for birefringence levels above ?0.005, and below, a plateau was observed. The shrinkage strain and stress were found to correlate well with the biaxial orientation factors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 487–496, 2003     

Influence of recycling and contamination on structure and transport properties of polypropylene

In this work the effect of three processing cycles on the physical properties of polypropylene (PP) was studied and related to the changes in the structure (molecular weight, molecular weight distribution, morphology) occurring during recycling. In order to simulate both the use and the recycling process of PP in the laboratory, PP pellets were contaminated with three model substances and submitted to three cycles of processing by injection molding. The bars for testing were produced from virgin and recycled polymers. The amount of degradation occurring during the reprocessing was estimated by means of viscosity and gel permeation chromatography measurements. Differential scanning calorimetry and scanning electron microscopy analyses were performed to investigate the crystallization behavior and the morphology of virgin and recycled PP. In order to obtain information on the structural organization and mobility of the amorphous phase, a dynamic mechanical thermal analysis and measurements of the transport properties were carried out. The results obtained were attributed to the different structural organization of the bars in relation to the number of processing cycles and contamination. Part of the work was focused on the recyclability of PP for food packaging applications, considering the residual contamination and migrational behavior after repeated processing cycles. In particular, the relationships existing between reprocessing, the residual amounts of contaminants, and the migrational behavior were investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1768–1778, 2003     

Effect of coupling agent on structure and properties of micro–nano composite fibers based on PET

Poly(ethylene terephthalate) (PET)/carbon black (CB) micro–nano composite fibers were manufactured by melt spinning method. To achieve good dispersion, nano‐CB particles were modified by coupling agent (CA). The effect of CA on structure and properties of the fibers were investigated via scanning electron microscopy (SEM), tensile testing, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), sonic orientation, and birefringence, respectively. At 2 wt % CA dosage, CB particles present the optimal dispersion in the fibers, shown in SEM images. Besides, the fibers possess the maximum breaking strength, the lowest crystallization temperature, and the highest crystallinity. After CA modification, the superior interfacial structure between PET and CB is beneficial to improve mechanical properties of the fibers. The well dispersed CB particles provide more heterogeneous nucleation points, resulting in the highest crystallinity. Furthermore, the fibers with 2 wt % CA dosage possess the maximum orientation and shrinkage ratio. According to Viogt–Kelvin model, the thermal shrinkage curves of the fibers can be well fitted using single exponential function. The three‐phase structure model of crystal phase–amorphous phase–CB phase was established to interpret the relationship among shrinkage, orientation, and dispersion of CB particles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43846.     

Structure and properties of composites of polyethylene or maleated polyethylene and cellulose or cellulose esters

Composites of linear low‐density poly(ethylene‐co‐butene) (PE) or maleated linear low‐density poly (ethylene‐co‐butene) (M‐PE) and cellulose (CEL), cellulose acetate (CA), cellulose acetate propionate (CAP), or cellulose acetate butyrate (CAB) were prepared in an internal laboratory mixer with 20 wt % polysaccharide. The structure and properties of the composites were studied with tensile testing, dynamic mechanical thermal analysis, differential scanning calorimetry, extraction with a selective solvent, Raman spectroscopy, and X‐ray diffraction. Composites prepared with M‐PE presented yield stress and elongation values higher than those of composites prepared with PE, showing the compatibilizer effect of maleic anhydride. Dynamic mechanical thermal analysis performed for M‐PE–CEL, M‐PE–CA, M‐PE–CAP, and M‐PE–CAB composites showed one glass‐transition temperature (T_g) close to that observed for pure M‐PE, and for M‐PE–CAP, another T_g lower than that measured for the polysaccharide was observed, indicating partial mutual solubility. These findings were confirmed by the extraction of one phase with a selective solvent, gravimetry, and Raman spectroscopy. X‐ray diffraction showed that the addition of CEL, CA, CAP, or CAB had no influence on the lattice constants of PE or M‐PE, but the introduction of the reinforcing material increased the amorphous region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:402–411, 2007     

Effects of equal‐channel,multiple‐angular extrusion on the physical and mechanical properties of glassy polymers

Through the examples of polycarbonate and poly(methyl acrylate), the evolution of the structure and properties of glassy polymers processed by equal‐channel multiple‐angular extrusion (ECMAE) were studied. It was demonstrated that ECMAE allowed the substantial improvement of the set of strain–strength characteristics of these materials, regardless of the direction of loading applied. With the use of the data from scanning electron microscopy, differential scanning calorimetry, and dilatometry, we found that the simultaneous growth in the strength, plasticity, and impact resistance was related to the formation of a net of biaxially oriented polymeric chains, the decrease in the free volume, and the reinforcement of intermolecular interaction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42180.     

Rheological properties of long chain branched polyethylene melts at high shear rate

Capillary extrusion experiments involving a number of polyethylenes with emphasis on assessing the effect of long chain branching (LCB) are performed. None of the metallocene catalyzed linear low density polyethylenes (mLLDPE) produced by Dow Chemicals, which are believed to have some level of LCB, show temperature dependence on the viscosity at the gross melt fracture regime. Furthermore, these materials do not show spurt or stick-slip flow, in contrast with most linear polyethylenes. LDPE and blends of LDPE with LLDPE having LCB also show the absence of stick-slip flow, but show temperature dependence on the viscosity. From these observations, we conclude that the stick-slip flow is very sensitive to the existence of LCB.     

Effect of vegetable‐based polyols in unimodal glass‐transition polyurethane slabstock viscoelastic foams and some guidance for the control of their structure–property behavior. II

Building on the dynamic mechanical analysis (DMA) characterization of the viscoelastic (VE) foam materials discussed in part I of this two‐part sequential series of articles, in this second part, we provide further information on the general physical properties of many of the same soy polyol and castor‐oil VE foams. In particular, the tensile, tear, elongation, indentation force deflection, support factor, compression set, hysteresis and ball‐rebound (resilience), and density properties are addressed in this article. The air flow and force buildup after compression deformation are also considered. Particular attention is also given to noting the degree of correlation of ball‐rebound behavior to that of the DMA damping data provided in part I. We concluded that when all of the properties of these vegetable‐based VE foams were taken as a whole, they had acceptable structure–property behaviors for VE applications, although certainly, the formulations could undoubtedly be further fine‐tuned for additional optimization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of vegetable‐based polyols in unimodal glass‐transition polyurethane slabstock viscoelastic foams and some guidance for the control of their structure–property behavior. I

We investigated the synthesis and structure–property behaviors of two types of vegetable‐oil polyols (soy oil and castor oil) and their use in viscoelastic (VE) polyurethane foams (PUFs). This article is the first in a two‐part series. In this initial part, we principally address the dynamic mechanical analysis (DMA) behavior of these foams in conjunction with information on the cellular morphology, sol fraction, and rise and reaction temperature profile behavior (the latter two parameters were determined during the foaming process). Particular emphasis is placed on the DMA damping characteristics, which represent one of the most critical parameters in the application of VE PUFs. It is also shown that the damping characteristics could be modified in such foams by the variation of the isocyanate/hydroxyl (×100) index, the addition of plasticizer, and in the case of soy polyols, the soy content. The frequency dependence of the VE PUFs is also briefly addressed. In the second article in this series, which directly follows this article, we further address the details of other relevant physical properties of these same foams in view of their applied nature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The hierarchical structure of water-assisted injection molded high density polyethylene: Small angle X-ray scattering study

High density polyethylene (HDPE) was molded by a new polymer processing method, that is, water-assisted injection molding (WAIM), and its hierarchical structure was studied by two-dimensional small angle X-ray scattering (SAXS). For comparison, the hierarchical structure of HDPE molded by conventional injection molding (CIM) was also characterized. The result shows that the WAIM part exhibits a distinct skin-core-water channel structure which is different from the skin-core structure for the CIM part. In the skin layer of both WAIM and CIM parts, the shish-kebab structure was formed due to the shear stress brought by melt filling, but the lamellar orientation parameter of CIM part is smaller than that of WAIM part. The spherulites with random lamellar orientation are dominant at the core of both parts owing to the low cooling rate and feeble shear stress therein. Interestingly, the shish structure and the lamellae with low level of orientation can be found at the water channel layer of WAIM part. They are attributed to the shear stress brought by water penetration. Moreover, the lamellar orientation parameter in water channel layer is smaller than that of skin layer. In addition, the long period of WAIM part first increases and then decreases with the elevating distance from the skin surface, while that of CIM part tends to increase monotonously. In a word, one can conclude that the rapid cooling rate and shear brought by the injected water have significant influence on the structural evolution for the WAIM part. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Diffusion mechanism of byproducts resulting from the peroxide crosslinking of polyethylene

In this study, a polyethylene grade used for applications in the insulation of energy cables was crosslinked by the peroxide crosslinking route. The impact of dicumyl peroxide (DCP) crosslinking on the polymer microstructure was studied. The different byproducts formed during the crosslinking reaction [acetophenone, α‐cumyl alcohol, and α‐methyl styrene (aMS)] were identified and quantified. Another molecule, 2,4‐diphenyl‐4‐methyl‐1‐pentene, regarded as an aMS dimer, was detected for the first time. Some amounts of residual DCP were also detected. A detailed study of the diffusion mechanism of each byproduct under different desorption conditions (e.g., samples exposed to vacuum or atmospheric conditions) and temperatures was performed. The diffusion coefficient values were determined and are discussed as a function of the desorption conditions and byproduct characteristics. Through this study, essential diffusion parameters were provided as a first step for further modeling development to allow the definition of optimized desorption conditions for a large range of sample geometries and thicknesses. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44525.