Prediction of nonlinear long‐term tensile creep of heterogeneous blends: Rubber‐toughened polypropylene–poly(styrene‐co‐acrylonitrile)

The proposed predictive format for the tensile compliance, D_b(t), of polymer blends is based on (1) a two‐parameter equivalent box model (EBM) and (2) calculations of the phase continuity of components in blends by using modified equations of the percolation theory. The input data encompass (1) selected parameters characterizing the creep of parent polymers and (2) critical volume fractions v_1cr and v_2cr of constituents in blends (delimiting the interval of phase cocontinuity). To describe the effects of time and stress on tensile compliance, a routinely used empirical equation was found suitable. Parameters characterizing the creep of parent polymers and their blends were extracted from generalized dependencies obtained through the superposition of time dependencies of tensile compliance assessed for a series of applied stresses and reconstructed with regard to the strain‐induced free‐volume expansion. Reconstructed dependencies can be approximated by a straight line, which simplifies the predictive format. The comparison of experimental and calculated compliance dependencies shows that the proposed format plausibly predicts the blend creep behavior over the studied interval of 0.1–10,000 min. The upswing in blend compliance after a long period of creeping is attributed to the redistribution of stresses acting on the constituents in the course of the creep under a constant load. This format is believed to have allowed the researchers in this study to anticipate (at least semiquantitatively) the creep behavior of intended blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 641–651, 2003     

Prediction of the gas permeability of heterogeneous polymer blends

A recently introduced predictive scheme is used to calculate the permeability of various types of heterogeneous polymer blends, which are characterized by the ratio of the permeability of constituents in the range 10–10,000. The scheme combines a two‐parameter equivalent box model and the data on the continuity of constituting phases acquired by modifying equations proposed by the percolation theory; it takes into account the permeability of components and the interval of phase duality (co‐continuity) delimited by the critical volume fractions of components v_1cr and v_2cr. The scheme can be used in two ways: (i) permeability of blends predicted by using the “theoretical” value of parameters v_1cr = v_2cr = 0.16 should be regarded as a first approximation which may not well approximate experimental data due to the fact that real v_1cr and v_2cr are affected by relative viscosities of the components, interfacial energy, conditions of blend mixing, phase structure coarsening, etc.; (ii) conversely, by fitting experimental data, it is possible to determine v_1cr and v_2cr for the studied system; thus the scheme can be alternatively viewed as an efficient tool for phase structure analysis of polymer blends.     

High‐density polyethylene/cycloolefin copolymer blends. Part 1: Phase structure,dynamic mechanical,tensile, and impact properties

High‐density polyethylene (HDPE) was blended with “reinforcing” cycloolefin copolymer (COC) in order to produce polyolefin materials with increased stiffness, yield and tensile strength. Experimental data on tensile modulus E_b, creep modulus E_bcr, storage modulus E_b′, loss modulus E_b″, yield strength S_yb, and tensile strength S_ub of blends are in plausible accord with their simultaneous prediction based on a predictive format that operates with a two‐parameter equivalent box model and the data on the phase continuity of components obtained from modified equations of the percolation theory. Dependencies of these mechanical properties on blend composition indicate the critical volume fraction v_2cr = 0.16 of COC. Interfacial adhesion in the HDPE/COC blends is strong enough to transmit acting stress up to the break point. Strain at break, tensile energy to break and tensile impact strength show conspicuous drops in the interval 15–25% of COC in the blends, during which COC starts to form a co‐continuous brittle component. Further growth of COC fraction accounts for reduction of blend ultimate properties to values typical of brittle polymers. However, tensile impact strength shows a local maximum at HDPE/COC = 25/75, which probably corresponds to COC toughened with HDPE particles. POLYM. ENG. SCI. 45:817–826, 2005. © 2005 Society of Plastics Engineers     

Polypropylene/elastomer/poly(styrene-co-acrylonitrile) blends: Manifestation of the critical volume fraction of SAN in dynamic mechanical, tensile and impact properties

The effect of the critical volume fraction v_cr of poly(styrene-co-acrylonitrile) (SAN) on the mechanical properties of its blends with rubber-toughened polypropylene (RTPP) containing about 12% grafted ethylene-propylene copolymer was studied. To encompass a wide spectrum of mechanical properties, blend components were selected which are characterized with rather different viscoelastic, tensile and ultimate properties. The SAN volume fraction in blends covers the interval 0∼0.30; concentration dependencies of measured mechanical properties indicate v_cr = 0.13. Experimental data on storage modulus E_b′, loss modulus E_b″, tensile modulus E_b, yield S_yb and tensile S_ub strength are in plausible accord with their simultaneous prediction based on a predictive scheme which operates with a two-parameter equivalent box model and the data on the phase continuity of components obtained from modified equations of the percolation theory. Strain at break, tensile energy to break and total impact energy of blends show a conspicuous drop in the interval 0∼15 % of SAN where SAN forms a discontinuous component; further growth of the SAN fraction accounts for a reduction of the blend ultimate properties to the values typical of brittle polymers.     

Phase structure coarsening in polymer blends: predicted effects of the phase duality interval on selected physical properties

A predictive scheme for simultaneous evaluation of the modulus, yield (or tensile) strength and gas permeability of heterogeneous polymer blends is used to estimate the effects of the phase duality interval delimited by the critical volume fractions of components v_1cr and v_2cr. The scheme combines a two‐parameter equivalent box model and the data on the phase continuity rendered by modified equations of the percolation theory. In addition to respective properties of constituents, the scheme also takes into account interfacial adhesion either sufficient or insufficient for stress transfer at yielding (or fracture). Simultaneously predicted properties of a blend are inter‐related through an identical set of input parameters characterizing a specific phase structure. It is schematically shown for model blends that narrowing of the phase duality interval due to phase structure coarsening accounts for a noticeable decrease in considered properties, particularly in yield (or tensile) strength if the interfacial adhesion is insufficient for the transfer of acting stress.     

Effect of the compatibility on dielectric performance and breakdown strength of poly(vinylidene fluoride)/low‐density polyethylene blends

Immiscible polymer blends with high dielectric constant (ε) and improved breakdown strength (E_b) performance were obtained by composing poly(vinylidene fluoride) (PVDF) with low‐density polyethylene (LDPE) or the LDPE grafted with maleic anhydride (LDPE‐g‐MAH) through melt‐blending way. The dielectric properties of these blends were emphasized for considering the compatibility effect on the energy storage application. Interface morphology, co‐continuity behavior, and grafted ratio were simultaneously investigated to detect the compatibility enhancement after introducing MAH. Results showed that the MAH positively improved the dielectric properties. Both the measured E_b of PVDF/LDPE and PVDF/LDPE‐g‐MAH blends showed a minimum value at v^PVDF = 50 vol % because of the worst compatibility; meanwhile, higher E_b of PVDF/LDPE‐g‐MAH than that of PVDF/LDPE blend was observed owing to the better compatibility. For considering the effect interface morphology on the dielectric performance, layer‐structure films composing with pure PVDF and LDPE layers were further constructed and studied. It was revealed that the layered structure could be treated as a helpful way to improve ε and E_b for immiscible polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42507.     

Stereocomplex formation between poly(L‐lactic acid) and poly(D‐lactic acid) with disproportionately low and high molecular weights from the melt

Poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) with very different weight‐average molecular weights (M_w) of 4.0 × 10³ and 7.0 × 10⁵ g mol^?1 (M_w(PDLA)/M_w(PLLA) = 175) were blended at different PDLA weight ratios (X_D = PDLA weight/blend weight) and their crystallization from the melt was investigated. The presence of low molecular weight PLLA facilitated the stereocomplexation and thereby lowered the cold crystallization temperature (T_cc) for non‐isothermal crystallization during heating and elevated the radial growth rate of spherulites (G) for isothermal crystallization, irrespective of X_D. The orientation of lamellae in the spherulites was higher for the neat PLLA, PDLA and an equimolar blend than for the non‐equimolar blends. It was found that the orientation of lamellae in the blends was maintained by the stereocomplex (SC) crystallites. Although the G values are expected to decrease with an increase in X_D or the content of high‐molecular‐weight PDLA with lower chain mobility compared with that of low‐molecular‐weight PLLA, G was highest at X_D = 0.5 where the maximum amount of SC crystallites was formed and the G values were very similar for X_D = 0.4 and X_D = 0.6 with the same enantiomeric excess. This means that the effect of SC crystallites overwhelmed that of chain mobility. The nucleating mechanisms of SC crystallites were identical for X_D = 0.1–0.5 in the T_c range 130–180 °C. Copyright © 2011 Society of Chemical Industry     

Short‐Term Morphology Relaxation of Thermoplastic Polyurethane Elastomers after Fast Strain Steps

Strain steps are applied to elastomers in a pneumatic relaxometer and monitored by small‐angle X‐ray scattering (SAXS). The relaxometer provides a rise time of 13 ms for strain pulses of step height Δε = ±1 in strain. The basic character of the 2D SAXS frames is examined and corresponding invariants Q(t) are analyzed. Three thermoplastic polyurethanes (TPU) of hardness 85 Shore A with different soft segments are studied both unannealed and annealed. The first response of all materials is a fast morphology conversion which finishes within t_mc =250 ms. Because it has been untraceable, it is characterized by a settling stroke Q(t_mc) ? Q(0). The second response is a slow morphology adjustment process which complies with logarithmic relaxation. It is characterized by a relaxation rate D_Q = Q(10 t)/Q(t) ? 1. Comparison indicates that the nanoscopic morphology relaxation processes appear to have little direct relation to the macroscopic stress relaxation curves. The materials differ with respect to hard‐domain morphology stability and morphology recovery. Most unstable is the morphology of the annealed polyether‐based material. It forms nanofibrillary entities when strained.     

Phase morphology and interfacial characteristics of polycarbonate/acrylonitrile‐ethylene‐propylene‐diene‐styrene blends compatibilized by styrene‐maleic anhydride copolymers

Blends of polycarbonate (PC) and acrylonitrile ‐ ethylene‐propylene‐diene‐styrene (AES) were reactive compatibilized by styrene‐maleic anhydride copolymers (SMA). The changes in phase morphology and interfacial characteristics of the blends as a function of maleic anhydride content of SMA and the concentration of compatibilizer have been systematic studied. The occurrence of reaction between the terminal hydroxyl groups of PC and the maleic anhydride (MA) of compatibilizer was confirmed by fourier transform infrared (FTIR) spectroscopy. A glass transition temperature (T_g) with an intermediate value between T_g(AES) and T_g(PC) was found on differential scanning calorimeter (DSC) curves of PC/AES blends compatibilized with SMA contains high levels of MA. Furthermore, at lower compatibilizer content, increase of the compatibilizer level in blends result in decreasing gap between two T_gs corresponding to the constituent polymers. Small angle X‐ray scattering (SAXS) test results indicated that compatibilizer concentration for the minimum of blend interface layer's thickness was exactly the same as it was when compatibilized PC/AES blend exhibited optimal compatibility in DSC test. The observed morphological changes were consistent well with the DSC and SAXS test results. A new mechanism of interfacial structural development was proposed to explain unusual phenomena of SMA compatibilized PC/AES blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42103.     

Shear creep resistance of styrene–isoprene–styrene (SIS)‐based hot‐melt pressure‐sensitive adhesives

The effects of the properties of substrates and tackifier on the shear creep of SIS‐based HMPSAs were investigated. The holding power (t_b) and shear adhesion failure temperature (SAFT) were measured. The relationship between the complex viscosity and the holding power was examined. The holding power and SAFT values of the triblock SIS blends were higher than those of the diblock‐containing SIS blends, perhaps because blends using triblock SIS have higher crossover temperature and complex viscosity than those using diblock‐containing SIS. Higher levels of aromatic resin‐modified aliphatic tackifier and rosin ester were found to decrease the holding power of the HMPSAs. This maybe due to the fact that rosin ester and aromatic‐modified aliphatic resin are compatible with both the ends and midblocks of SIS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 825–831, 2006     

Phenolic wastewater treatment in a three‐phase fluidised bed bioreactor containing low density particles

The treatment of phenolic wastewater was investigated in a gas–liquid–solid fluidised bed bioreactor containing polypropylene particles of density 910 kg m^?3. Measurements of chemical oxygen demand (COD) versus residence time (t) were performed for various ratios of settled bed volume to bioreactor volume (V_b/V_R) and air velocities (u) to determine the values of (V_b/V_R) and u for which the largest reduction in COD occurred. Optimal operation, corresponding to the largest COD removal, was attained when the bioreactor was controlled at the ratio (V_b/V_R) = 0.55 and an air velocity u = 0.036 m s^?1. Under these conditions, the value of COD was practically at steady state for times greater than 50 h. At this steady state, only about 50% COD removal was achieved in the treatment of a ‘raw’ wastewater (no mineral salts added), whereas in the operation with wastewater enriched in nutrient salts approximately 90% COD removal was attained. The following amount of mineral salts (mg dm^?3): (NH₄)₂SO₄—500; KH₂PO₄—200; MgCl₂—30; NaCl—30; CaCl₂—20; and FeCl₃—7, when added to wastewater before treatment, was sufficient for biomass growth. The application of low density particles (used as biomass support) in a bioreactor allowed the control of biomass loading in the apparatus. In the cultures conducted after change in (V_b/V_R) at a set u, the steady state mass of cells grown on the particles was achieved after approximately 6 days of operation. With change in u at a set (V_b/V_R), the new steady state biomass loading occurred after culturing for about 2 days. Phenolic wastewater was successfully treated in a bioreactor. In the operation conducted in a bioreactor optimally controlled at (V_b/V_R) = 0.55, u = 0.036 m s^?1 and t = 50 h, conversions greater than 99% were achieved for all phenolic constituents of the wastewater. Conversions of about 90% were attained for other hydrocarbons. Copyright © 2005 Society of Chemical Industry     

Probe dependency of polymer‐plasticizer and polymer‐polymer interaction parameters in inverse gas chromatography

Inverse gas chromatography has been widely used to determine the Flory–Huggins parameter, χ, between a plasticizer and a polymer, or between two polymers. Many studies showed that interaction parameters may be probe dependent. In a recent study it was proposed that, when a specific interaction occurred between two polymers, the probes had less interaction with the polymers, leading to a lower solubility parameter for polymer blends than the volume average of the components. An equation was derived to relate the probe dependency to the deviation of solubility parameter of polymer mixtures. Here this approach is applied to plasticized poly(vinyl chloride) (PVC) and a copolymer, and to poly(vinylidene fluoride)–poly(ethyl methacrylate) blends. For a PVC and epoxidized oil system the relative deviation of specific retention volume showed two trends, with saturated hydrocarbons as one group, and polar and aromatic probes as another group. For the poly(vinylidene fluoride)/poly(ethyl methacrylate) system the plot of retention volume deviation versus solubility parameter of probes also showed separate trends for n‐alkanes, esters, and alcohols. But the plot of ?₂?₃RT(χ₂₃/V₂) versus solubility parameter had better linearity for the systems studied. The slope of this plot was used as an indicator for miscibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nonlinear phase‐separation behavior of poly(methyl methacrylate)/poly(styrene‐co‐maleic anhydride) blends

The nonlinear phase‐separation behavior of poly(methyl methacrylate)/poly(styrene‐co‐maleic anhydride) (PMMA/SMA) blends over wide appropriate temperature and heating rate ranges was studied using time‐resolved small‐angle laser light scattering. During the non‐isothermal process, a quantitative logarithm function was established to describe the relationship between cloud point (T_c) and heating rate (k) as given by T_c = Alnk + T₀, in which the parameter A, reflecting the heating rate dependence, is much different for different compositions due to phase‐separation rate and activation energy difference. For the isothermal phase‐separation process, an Arrhenius‐like equation was successfully applied to describe the temperature dependence of the apparent diffusion coefficient (D_app) and the relaxation time (τ) of the early stage as well as the late stage of spinodal decomposition (SD) of PMMA/SMA blends. Based on the successful application of the Arrhenius‐like equation, the related activation energies could be obtained from D_app and τ of the early and late stages of SD, respectively. In addition, these results indicate that it is possible to predict the temperature dependence of the phase‐separation behavior of binary polymer mixtures during isothermal annealing over a range of 100 °C above the glass transition temperature using the Arrhenius‐like equation. © 2012 Society of Chemical Industry     

Morphology and mechanical properties of polypropylene/high‐impact polystyrene blends from postconsumer plastic waste

The compatibilizing effect of the triblock copolymer poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) on the morphological and mechanical properties of virgin and recycled polypropylene (PP)/high‐impact polystyrene (HIPS) blends was studied, with the properties optimized for rigid composite films. The components of the blend were obtained from municipal plastic waste, PP being acquired from mineral water bottles (PP_b) and HIPS from disposable cups. These materials were preground, washed only with water, dried with hot air, and ground again (PP_b) or agglutinated (HIPS). Blends with three different weight ratios of PP_b and HIPS (6:1, 6:2, and 6:3) were prepared, and three different concentrations of SEBS (5, 6, and 7 wt %) were used for investigations of its compatibilizing effect. Scanning electron microscopy showed that SEBS reduced the diameter of dispersed HIPS particles in the globular and fibril shapes and improved the adhesion between the disperse phase and the matrix. However, SEBS interactions with PP_b and HIPS influenced the mechanical properties of the compatibilized PP_b/HIPS/SEBS blends. An adequate composition of PP/HIPS, for both virgin and recycled blends, for applications in composite films with characteristics similar to those of synthetic paper was obtained with a minimal amount of SEBS and a maximal HIPS/PP ratio in the range of concentrations studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2861–2867, 2003     

Effect of scale‐up on wall shear rates in circulating bubble columns

Effective wall shear rates were investigated experimentally in an external loop circulating bubble column made from transparent acrylic resin. The riser (D_R) and downcomer (D_D) diameters were 0.19 m and 0.14 m, respectively. The column working volume (V_R) was 170 dm³, with a scale‐up factor (A_D/A_R) of 0.54, and a dispersion height (H_D) of 2.25 m. Polymer solutions of xanthan gum and carboxymethyl cellulose were used to simulate non‐Newtonian behavior of biological systems. Effective wall shear rates for the non‐Newtonian solutions were found by analogy with Newtonian glycerol solutions, employing downcomer liquid velocity as the measurable and comparable parameter. The experimental shear rate results were found to fit between those of the literature data. A new single correlation taking into account all the relevant data in the literature and the results of this work is proposed. The new correlation is an improvement over the other correlations because it includes two important design constants: scale‐up factor and dispersion height. Copyright © 2005 Society of Chemical Industry     

Features of the Structure and Properties of Radiation Vulcanizates Based on Blends of Polybutadiene and Ethylene‐Propylene Diene Rubber

Polybutadiene rubber (BR) was blended with ethylene‐propylene diene (EPDM) rubber on rubber mill with different weight ratios (100/0‐70/30‐50/50‐30/70‐0‐100), then application of gamma rays at different irradiation doses from 25 up to 150 kGy to induce crosslinking. Mechanical, physio‐chemical, and characterization of prepared blends are to be followed up as functions of the blend composition and the radiation absorbed dose. Mechanical properties like tensile strength (TS), elongation at break (E_b), and tensile modulus (M₁₀₀) were increased with increasing content of EPDM in blend composition. On the other hand, TS and M₁₀₀ increased with radiation dose, whereas the value of E_b decreased with radiation dose. Physico‐chemical properties like gel fraction and volume fraction of rubber in swollen gel (V_r) increased with increasing the content of EPDM rubber in blend formulation while the swelling ratio and soluble fraction decreased with increasing content of EPDM. On the other hand, the V_r increased with radiation dose, whereas the values of soluble fraction and selling ratio (Q) decreased with radiation dose. Fourier transforms‐infrared measurements confirmed the compatibility between BR and EPDM rubber moieties in the blend matrix. J. VINYL ADDIT. TECHNOL., 25:E64–E72, 2019. © 2018 Society of Plastics Engineers     

Crystallization behavior of PEO in blends of poly(ethylene oxide)/poly(2‐vinyl pyridine)‐b‐(ethylene oxide) block copolymer

The crystallization behavior of two molecular weight poly(ethylene oxide)s (PEO) and their blends with the block copolymer poly(2‐vinyl pyridine)‐b‐poly(ethylene oxide) (P2VP‐b‐PEO) was investigated by polarized optical microscopy, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy (AFM). A sharp decreasing of the spherulite growth rate was observed with the increasing of the copolymer content in the blend. The addition of P2VP‐b‐PEO to PEO increases the degradation temperature becoming the thermal stability of the blend very similar to that of the block copolymer P2VP‐b‐PEO. Glass transition temperatures, T_g, for PEO/P2VP‐b‐PEO blends were intermediate between those of the pure components and the value increased as the content of PEO homopolymer decreased in the blend. AFM images showed spherulites with lamellar crystal morphology for the homopolymer PEO. Lamellar crystal morphology with sheaf‐like lamellar arrangement was observed for 80 wt% PEO(200M) and a lamellar crystal morphology with grain aggregation was observed for 50 and 20 wt% blends. The isothermal crystallization kinetics of PEO was progressively retarded as the copolymer content in the blend increased, since the copolymer hinders the molecular mobility in the miscible amorphous phase. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Synthesis,Crystal Structure,and Thermal Behaviors of 3‐Nitro‐1,5‐bis(4,4′‐dimethylazide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP)

The energetic material, 3‐nitro‐1,5‐bis(4,4′‐dimethyl azide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP), was firstly synthesized by means of Click Chemistry using 1,5‐diazido‐3‐nitrazapentane as main material. The structure of NDTAP was confirmed by IR, ¹H NMR, and ¹³C NMR spectroscopy; mass spectrometry, and elemental analysis. The crystal structure of NDTAP was determined by X‐ray diffraction. It belongs to monoclinic system, space group C2/c with crystal parameters a=1.7285(8) nm, b=0.6061(3) nm, c=1.6712(8) nm, β=104.846(8)°, V=1.6924(13) nm³, Z=8, μ=0.109 mm⁻¹, F(000)=752, and D_c=1.422 g cm⁻³. The thermal behavior and non‐isothermal decomposition kinetics of NDTAP were studied with DSC and TG‐DTG methods. The self‐accelerating decomposition temperature and critical temperature of thermal explosion are 195.5 and 208.2 °C, respectively. NDTAP presents good thermal stability and is insensitive.     

Multinuclear solid‐state NMR investigation of the moisture distribution in PEEK‐PBI and PEKK‐PBI blends

Blends of polyaryletherketones (PAEK), such as polyetheretherketones (PEEK) and polyetherketoneketones (PEKK), with polybenzimidazole (PBI) are of commercial interest due to their improved high‐temperature stability and wear properties. The changes of PBI and its PEEK‐ and PEKK‐blends (50 : 50 wt %) after immersing them in liquid H₂O and D₂O, and exposing them to D₂O steam at elevated temperatures and pressures are investigated by multinuclear solid‐state NMR and IR spectroscopy. Macroscopic morphological and chemical changes on the molecular scale, which take place upon high‐temperature steam‐treatment and the extent and reversibility of moisture uptake have been investigated. Interactions and reactions of water, steam, and aqueous solutions of LiCl and ZnBr₂ with the functional groups of the polymer components have been studied using D₂O in combination with IR, ¹H wideline, ²H, ⁷Li, and ⁷⁹Br MAS, as well as ¹³C and ¹⁵N CP/MAS NMR spectroscopy. Different locations and types of water and protons in the blends have been described and PBI has been proven to be mainly responsible for water and salt uptake into the blends. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41421.