Rheological behavior of high‐density polyethylene (HDPE) filled with paper mill sludge

A comparative study was conducted of composites made with sludge from three different paper mills. Sludges were obtained from a thermomechanical pulp (TMP), a chemico‐TMP (CTMP), and a Kraft mill with a feedstock of primarily black spruce. The primary sludge (PS) and secondary sludge (SS) were mixed at two different ratios (PS:SS = 7:3 and 9:1) and blended with high‐density polyethylene (HDPE) at 20%, 30%, and 40% proportion. The blends were tested using plate–plate geometry before subjection to frequency sweep by oscillation rheometry. The storage modulus (G′), loss modulus (G″), and complex viscosity (η*) increased with increasing paper sludge content. Decreasing the PS:SS ratio from 9:1 to 7:3 decreased G′, G″, and η*. Differential scanning calorimetry showed that sludge addition increased both the melting and crystallization temperature, for a positive effect on crystallinity. Although the behavior of sludge–high‐density polyethylene blends differed from that of traditional wood plastic composite made with wood flour, they obtained G′, G″, and η* values of the same magnitude. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46484.     

Degradation behaviors of linear low‐density polyethylene and poly(L‐lactic acid) blends

In this study, the degradability of linear low‐density polyethylene (LLDPE) and poly(L ‐lactic acid) (PLLA) blend films under controlled composting conditions was investigated according to modified ASTM D 5338 (2003). Differential scanning calorimetry, X‐ray diffraction, and Fourier transform infrared spectroscopy were used to determine the thermal and morphological properties of the plastic films. LLDPE 80 (80 wt % LLDPE and 20 wt % PLLA) degraded faster than grafted low‐density polyethylene–maleic anhydride (M‐g‐L) 80/4 (80 wt % LLDPE, 20 wt % PLLA, and 4 phr compatibilizer) and pure LLDPE (LLDPE 100). The mechanical properties and weight changes were determined after composting. The tensile strength of LLDPE 100, LLDPE 80, and M‐g‐L 80/4 decreased by 20, 54, and 35%, respectively. The films, as a result of degradation, exhibited a decrease in their mass. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal analysis of high‐density polyethylene and low‐density polyethylene with enhanced biodegradability

The thermal properties of high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) filled with different biodegradable additives (Mater‐Bi AF05H, Cornplast, and Bioefect 72000) were investigated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The DSC traces of the additives indicated that they did not undergo any significant phase change or transition in the temperature region typically encountered by a commercial composting system. The TGA results showed that the presence of the additive led to a thermally less stable matrix and higher residue percentages. The products obtained during the thermodegradation of these degradable polyolefins were similar to those from pure polyethylenes. The LDPE blends were thermally less stable than the HDPE blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 764–772, 2002     

Statistical and kinetic approaches for linear low‐density polyethylene melting modeling

The aim of this study was to compare different models, either originating from literature or originally proposed in this study, for the interpretation of the melting behavior of polymers. In particular, these models, tested with a linear low‐density polyethylene widely used in rotational molding, are suitable for coupling with energy balances in the study of polymer processing. We obtained the experimental data from differential scanning calorimetry (DSC) dynamic scans, assuming that the endothermic flux was related to the rate of melting of the polymer. The studied models were able to predict the broad melting temperature range typically observed during polymer melting with either a statistical or a kinetic approach. The two different approaches were compared with experimental DSC data. The analysis of model performances with complex thermal programs showed that the statistical approach could provide a more realistic representation of polymer melting. These models were particularly suitable in rotational molding, where the lack of any flow and, hence, of any crystalline orientation leads to a degree of melting determined by the actual temperature of the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 289–295, 2003     

Calendered linear low‐density polyethylene consolidated meat and bone meal composites

Bioplastics produced from meat and bone meal (MBM) suffer from rapid and drastic mechanical property deterioration because of their hydrophilic nature. This study investigates mechanical and water stability of composites produced from introduction of a minor component of a synthetic polyethylene as a binder phase to consolidate MBM. The milled and sieved MBM was compounded with 5–60 wt % linear low‐density polyethylene (LLDPE) and formed into composite sheets by calendering, which is an industrially relevant process. Results indicated that a minimum of 15 wt % LLDPE content was required to form a nominally continuous binder phase that allowed for good processability and environment stability of the composites. As expected, the water vapor permeability (WVP) and water absorption characteristics of the composites were intermediate between those of MBM and LLDPE. Sheets containing 15 wt % LLDPE absorbed up to 35 wt % water. Composites tested after being soaked in water showed an initial decrease in TS of about 30% for the first hour but then remained fairly unchanged in the next 72 hours, confirming their moderate environment stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41145.     

Chemical and thermal characterization of high‐ and low‐density irradiated polyethylenes

A comparative study of the dynamic mechanical relaxation spectra of high‐ and low‐density polyethylenes irradiated with γ‐radiation from a Co⁶⁰ source was performed. The irradiation doses ranged from 0 to 100 Mrad. All the samples were previously characterized by determination of the molecular weight distribution, the number of functional groups, and the crystalline fraction. All the relaxation zones between ?145°C and the melt were studied in the frequency range from 0.3 to 30 Hz. The changes observed in the mechanical relaxation spectra were related to modifications in the chemical structure and morphological parameters attributed to the exposure of the samples to the γ‐radiation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1953–1958, 2002     

Melt miscibility and mechanical properties of metallocene linear low‐density polyethylene blends with high‐density polyethylene: influence of comonomer type

In this paper, the implications of melt miscibility on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)/high‐density polyethylene (HDPE) blends were assessed with respect to the influence of the comonomer type. The influence of the latter was examined by selecting one butene LLDPE and one octene LLDPE of very similar weight‐average molecular weight (M_w), molecular‐weight distribution (MWD) and branch content, keeping the comonomer type as the only primary molecular variable. Each of the two metallocene LLDPEs was melt‐blended with the same HDPE at 190 °C in a Haake melt‐blender. The rheological, thermal and mechanical properties were measured by the use of an ARES rheometer, differential scanning calorimeter and Instron machine, respectively. The rheological measurements, made over the linear viscoelastic range, suggested no significant influence of the branch type on the melt miscibility. The rheology results are in agreement with those obtained from previous transmission electron microscopy (TEM) and small‐angle neutron scattering (SANS) studies. The dynamic shear viscosity and total crystallinity of the metallocene (m)‐LLDPE blends with HDPE followed linear additivity. At small strains, the branch type has little or no influence on the melt miscibility and solid‐state properties of the blends. Even the large‐strain mechanical properties, such as tensile strength and elongation at break, were not influenced by the comonomer type. However, the ultimate tensile properties of the HDPE‐rich blends were poor. Incompatibility of the HDPE‐rich blends, as a result of the weak interfaces between the blend components, is suggested to develop at large strains. Copyright © 2005 Society of Chemical Industry     

Compatibility study of chlorinated polyethylene/ethylene methacrylate copolymer blends using thermal,mechanical, and chemical analysis

Blends of chlorinated polyethylene (CPE) elastomer and ethylene methacrylate copolymer (EMA) in various compositions were studied for their compatibility using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared (FTIR) spectroscopy techniques. Irrespective of measurement techniques used, all blends showed a single glass transition temperature (T_g) lying in between the T_g of control polymers in both DSC and DMA. Glass transition temperatures of blends obtained from DSC were in consistency with Couchman–Karasz equation. Also, the T_g obtained from both DSC and DMA are above the “rule of mixing” line of the two control polymers. These results from thermal analysis clearly indicate some compatibility between the two polymers. Furthermore, compatibility of CPE/EMA blends were also been investigated by FTIR spectroscopy and scanning electron microscopic analysis. A shifting of characteristic C? Cl stretching peak of CPE and C?O stretching peak of EMA toward lower wave number indicate the presence of specific interaction between the two polymers. Mechanical properties like tensile strength, modulus at 100% elongation, elongation at break, and hardness were observed above the line of additivity drawn between the two control polymers, which corroborate compatibility between CPE and EMA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40316.     

Rheological and morphological properties of high‐density polyethylene and poly(ethylene–octene) blends

The rheological and morphological properties of blends based on high‐density polyethylene (HDPE) and a commercial ethylene–octene copolymer (EOC) produced by metallocene technology were investigated. The rheological properties were evaluated in steady and dynamic shear experiments at 190°C in shear rates ranging from 90 s^?1 to 1500 s^?1 and frequency range between 10^?1 rad/s and 10² rad/s, respectively. These blends presented a high level of homogeneity in the molten state and rheological behavior was generally intermediate to those of the pure components. Scanning electron microscopy (SEM) showed that the blends exhibit dispersed morphologies with EOC domains distributed homogeneously and with particle size inferior to 2 μm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2240–2246, 2002     

Melt strength of linear low‐density polyethylene/low‐density polyethylene blends

Linear low‐density polyethylenes and low‐density polyethylenes of various compositions were melt‐blended with a batch mixer. The blends were characterized by their melt strengths and other rheological properties. A simple method for measuring melt strength is presented. The melt strength of a blend may vary according to the additive rule or deviate from the additive rule by showing a synergistic or antagonistic effect. This article reports our investigation of the parameters controlling variations of the melt strength of a blend. The reciprocal of the melt strength of a blend correlates well with the reciprocal of the zero‐shear viscosity and the reciprocal of the relaxation time of the melt. An empirical equation relating the maximum increment (or decrement) of the melt strength to the melt indices of the blend components is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1408–1418, 2002     

Compatibility of low‐density polyethylene/poly(ethylene‐co‐vinyl acetate) binary blends prepared by melt mixing

The compatibility of low‐density polyethylene and poly(ethylene‐co‐vinyl acetate) containing 18 wt % vinyl acetate units (EVA‐18) was studied. For this purpose, a series of different blends containing 25, 50, or 75 wt % EVA‐18 were prepared by melt mixing with a single‐screw extruder. For each composition, three different sets of blends were prepared, which corresponded to the three different temperatures used in the metering section and the die of the extruder (140, 160, and 180°C), at a screw rotation speed of 42 rpm. Blends that contained 25 wt % EVA‐18 were also prepared through mixing at 140, 160, or 180°C but at a screw speed of 69 rpm. A study of the blends by differential scanning calorimetry showed that all the prepared blends were heterogeneous, except that containing 75 wt % EVA‐18 and prepared at 180°C. However, because of the high interfacial adhesion, a fine dispersion of the minor component in the polymer matrix was observed for all the studied blends with scanning electron microscopy. The tensile strengths and elongations at break of the blends lay between the corresponding values of the two polymers. The absence of any minimum in the mechanical properties was strong evidence that the two polymers were compatible over the whole range of composition. The thermal shrinkage of the blends at various temperatures depended mainly on the temperature and EVA‐18 content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 841–852, 2003     

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     

Nonisothermal crystallization kinetics of linear bimodal–polyethylene (LBPE) and LBPE/low‐density polyethylene blends

Nonisothermal crystallization kinetics of linear bimodal–polyethylene (LBPE) and the blends of LBPE/low‐density polyethylene (LDPE) were studied using DSC at various scanning rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of LBPE and LBPE/LDPE blends. The theory of Ozawa was also used to analyze the LBPE DSC data. Kinetic parameters such as, for example, the Avrami exponent (n), the kinetic crystallization rate constant (Z_c), the crystallization peak temperature (T_p), and the half‐time of crystallization (t_1/2) were determined at various scanning rates. The appearance of double melting peaks and double crystallization peaks in the heating and cooling DSC curves of LBPE/LDPE blends indicated that LBPE and LDPE could crystallize, respectively. As a result of these studies, the Z_c of LBPE increases with the increase of cooling rates and the T_p of LBPE for LBPE/LDPE blends first increases with increasing LBPE content in the blends and reaches its maximum, then decreases as the LBPE content further increases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2431–2437, 2003     

Rheological and thermal properties of poly(ethylene oxide)/multiwall carbon nanotube composites

Poly(ethylene oxide) (PEO) based nanocomposites were prepared by the dispersion of multiwall carbon nanotubes (MWCNTs) in aqueous solution. MWCNTs were added up to 4 wt % of the PEO matrix. The dynamic viscoelastic behavior of the PEO/MWCNT nanocomposites was assessed with a strain‐controlled parallel‐plate rheometer. Prominent increases in the shear viscosity and storage modulus of the nanocomposites were found with increasing MWCNT content. Dynamic and isothermal differential scanning calorimetry studies indicated a significant decrease in the crystallization temperature as a result of the incorporation of MWCNTs; these composites can find applications as crystallizable switching components for shape‐memory polymer systems with adjustable switching temperatures. The solid‐state, direct‐current conductivity was also enhanced by the incorporation of MWCNTs. The dispersion level of the MWCNTs was investigated with scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheological properties and morphology of compatibilized poly(butylene terephthalate)/linear low‐density polyethylene alloy

The rheological behavior of PBT/LLDPE and PBT/LLDPE‐g‐AA blends [where PBT is poly(butylene terephthalate), LLDPE is linear low‐density polyethylene, and AA is acrylic acid] under a capillary flow was investigated with a capillary rheometer. The Utracki equation was used to describe the viscosity–composition dependence of PBT/LLDPE and PBT/LLDPE‐g‐AA blends at low shear stresses. However, at high shear stresses, this equation was not suitable for these blending systems. There existed a maximum on the curves of the entrance pressure drop versus the blending compositions, and the interlayer slip factor β in the Utracki equation was related not only to the shear stress but also to the elasticity difference of the two blending components. Morphological observations indicated that at high shear rates, there existed two different morphologies at different positions of the extrudates, and this was the reason that the Utracki equation failed. Near the wall of the capillary, low‐viscosity PBT stratified, and this resulted in an additional decrease in the viscosities of the blending systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 206–213, 2003     

Mechanical and thermo‐physical properties of high‐density polyethylene modified with talc

The aim of this study was to examine the physical, mechanical, and thermo‐physical properties of high‐density polyethylene (HDPE) modified with talc. Different weight fractions of talc (up to 35 wt %) were compounded with an HDPE matrix containing 2.5 wt % of carbon black (CB) in a twin‐screw compounder. The composites were then processed by injection moulding to obtain specimens for testing. The results indicate that CB causes a significant decrease in the toughness, while talc not only enhances the thermal conductivity and thermo‐physical properties of the composites but can also play a role in compensating for the negative effects of CB on impact resistance. The experimental data show that the presence of CB reduces the impact resistance of HDPE by up to 34%, while addition of up to 8 wt % talc can return this value to close to that of pure HDPE. No significant effect on the composite tensile yield and fracture strength was observed for either component at all concentrations. The thermal conductivity, thermal diffusivity, and specific density values of the composites increased almost linearly, but the increase in moisture absorption in the long term showed nonlinear behavior in the concentration range of the experiment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly(L‐lactide)/polypropylene blends: Evaluation of mechanical,thermal, and morphological characteristics

Poly(L lactide) (PLA) was blended with polypropylene (PP) at various ratios (PLA:PP = 90 : 10, 80 : 20, 70 : 30, and 50 : 50) with a melt‐blending technique in an attempt to improve the melt processability of PLA. Maleic anhydride (MAH)‐grafted PP and glycidyl methacrylate were used as the reactive compatibilizers to induce miscibility in the blend. The PLA/PP blend at a blend ratio of 90 : 10, exhibited optimum mechanical performance. Differential scanning calorimetry and thermogravimetric analysis studies showed that the PLA/PP/MAH‐g‐PP blend had the maximum thermal stability with the support of the heat deflection temperature values. Furthermore, dynamic mechanical analysis findings revealed an increase in the glass‐transition temperature and storage modulus with the addition of MAH‐g‐PP compatibilizer. The interaction between the compatibilizers and constituent polymers was confirmed from Fourier transform infrared spectra, and scanning electron microscopy of impact‐fractured samples showed that the soft PP phase was dispersed within the PLA matrix, and a decrease in the domain size of the dispersed phase was observed with the incorporation of MAH‐g‐PP, which acted as a compatibilizer to improve the compatibility between PLA and PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Wood particle/high‐density polyethylene composites: Thermal sensitivity and nucleating ability of wood particles

The thermal sensitivity, nucleating ability, and nonisothermal crystallization of high‐density polyethylene (HDPE) with different wood fillers during wood/HDPE melt processing were investigated with thermogravimetric analysis and differential scanning calorimetry. The results showed that the wood degraded at a lower temperature than HDPE. The thermal decomposition behavior was similar across wood species. The most remarkable dissimilarities were observed between wood and bark in the decomposition rate around a processing temperature of 300°C and in the peak temperature location for cellulose degradation. The higher degradation rate for bark was explained by the devolatilization of extractives and the degradation of lignin, which were present in higher amounts in pine bark. The nucleating ability for various wood fillers was evaluated with the crystalline weight fraction, crystal conversion, crystallization half‐time, and crystallization temperature of the HDPE matrix. The nucleation activity improved with the addition of wood particles to the HDPE matrix. However, no effect of wood species on the crystal conversion was found. For composites based on semicrystalline matrix polymers, the crystal conversion may be an important factor in determining the stiffness and fracture behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of branching characteristics on thermal and mechanical properties of Ziegler–Natta and metallocene hexene linear low‐density polyethylene blends with low‐density polyethylene

The effect of the branch content (BC) and composition distribution (CD) of linear low‐density polyethylene (LLDPE) on the thermal and mechanical properties of its blends with LDPE were studied. All blends and pure resins were conditioned in a Haake PolyDrive blender at 190°C and in the presence of adequate amounts of antioxidant. Two metallocene LLDPEs (m‐LLDPE) and one Ziegler–Natta (ZN) hexene LLDPE were melt blended with the same LDPE. The effect of the BC was investigated by blending two hexene m‐LLDPEs of similar weight‐average molecular weights and molecular weight distributions but different BCs with the same LDPE. The effect of the CD was studied by using a ZN and an m‐LLDPE with similar weight‐average molecular weights, BCs, and comonomer type. Low‐BC m‐LLDPE blends showed separate crystallization whereas cocrystallization was observed in the high‐BC m‐LLDPE‐rich blends. However, ZN‐LLDPE/LDPE blends showed separate crystallization together with a third population of cocrystals. The influence of the crystallization behavior was reflected in the mechanical properties. The BC influenced the modulus, ultimate tensile strength, and toughness. The addition of a small amount of LDPE to a low‐BC m‐LLDPE resulted in a major improvement in the toughness, whereas the results for the high‐BC pair followed the additivity rule. ZN‐LLDPE blends with LDPE blends were found to be more compatible and exhibited superior mechanical properties compared to m‐LLDPE counterparts with the same weight‐average molecular weight and BC. All mechanical properties of ZN‐LLDPE blends follow the linear rule of mixtures. However, the CD had a stronger influence on the mechanical properties in comparison to the BC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2488–2498, 2005     

Viscoelasticity and morphology of poly(ethylene‐co‐vinyl acetate)/polyisobutylene blends

Blends of an ethylene/vinyl acetate copolymer (EVA) and polyisobutylene of various compositions were prepared by mechanical mixing at a temperature above the melting point of EVA (T_m^EVA) but below the upper critical solution temperature of 170°C for given blends. The rheological properties of the components and blends were studied in the region of small‐amplitude oscillating deformation at temperatures above and below T_m^EVA in the frequency range of 0.01–100 rad/s. At temperatures lower than T_m^EVA, the rheological properties were determined by the existence of the yield stress. With diminishing frequency, the viscosity increased, and the plateau in the relaxation spectrum at low frequencies broadened. The morphology of the blends depended on the conditions of sample heating. The introduction of a finely dispersed filler into the blends led to an anomalous drop in the viscosity. The morphology of the systems that arose by mechanical blending of the molten components was the important factor in the rheological behavior. The observed effects were examined in the framework of the concept of structural networks formed in melts by nonmelted crystallites of EVA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2700–2707, 2006