Polybenzimidazole (PBI) molecular weight and Mark‐Houwink equation

The molecular weight, and intrinsic viscosity of polybenzimidazole (PBI) and its phosphonylated derivatives are reported. The relationship between intrinsic viscosity [η] and weight average molecular weight (M_w) for PBI has been established in H₂SO₄ and DMF‐LiCl. The Mark Houwink constants K_w of 5.2 × 10^?3 mL/g, α of 0.92 for H₂SO₄ solvent systems and, K_w of 3.2 × 10^?2 mL/g, α of 0.754 for DMF‐LiCl solvent system have been determined at M_w < 65,000. The intrinsic viscosity of PBI determined by the Huggins–Kraemer method was compared with a single point method, and found that both methods fit well for PBI in relatively low concentration solvent system, giving ～ 99% accuracy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel,rosin‐based,hydrophobically modified cationic polyacrylamide for kaolin suspension flocculation

A novel, hydrophobically modified cationic polyacrylamide (HMPAM) was synthesized via the copolymerization of acrylamide, diallyl dimethyl ammonium chloride (DMDAAC), and diallylmethyl dehydroabietic acid propyl ester ammonium bromide. Optimum conditions for preparing HMPAM were such that the amount of initiator was 0.075 wt % of the total monomer mass, the monomer concentration was 20 wt %, and the amount of DMDAAC was 18 mol % of the total monomer molar mass. HMPAM was characterized with an UV–visible spectrometer, ¹H‐NMR, Ubbelohde viscometer, rotational viscometer, and rotational rheometer. HMPAM solutions exhibited strong hydrophobic associations, and the critical association concentration of the HMPAM aqueous solution was about 0.7 wt %; the HMPAM solutions also showed salt thickening and shear resistance. The surface morphologies of the freeze‐dried HMPAM samples (1 wt %) were also observed via scanning electron microscopy. Compared with unmodified cationic polyacrylamide, Synthesis of HMPAM‐0.5 exhibited a stronger flocculation capacity, and the optimal transmittance of the supernatants was above 95%. HMPAM‐0.5 showed significant flocculation performances for 3–4 and 3–5 wt % kaolin suspensions at 40 and 50 mg/L, respectively. Moreover, the flocculation performance was enhanced with the addition of NaCl and CaCl₂. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46637.     

Viscoelastic properties and structure of poly(acrylonitrile‐co‐methacrylic acid) polymer solutions for gel spinning at long aging times

The objective of the research is to obtain a more complete understanding of how aging affects the viscoelastic properties of polymer solutions to be used as starting materials for gel spinning of polymer fibers. Specifically, poly(acrylonitrile‐co‐methacrylic acid) solutions were prepared and characterized using rheological measurements and nuclear magnetic resonance spectroscopy. The results indicate that elastic character increased with increasing polymer concentration and that gelation of these solutions continued up to aging times of several weeks. Additionally, comparing the results from the two characterization methods show that while gelation continues to occur, the viscoelastic properties decrease after a critical time point suggesting that a chemical change occurs in the solutions at long times. However, these changes impact the solution dynamics minimally as the effective network properties were similar at the aging times studied here, but considerations for long‐term storage of polymer solutions for gel spinning are warranted. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39821.     

Oxidation resistance and abrasive wear resistance of vitamin E stabilized radiation crosslinked ultra‐high molecular weight polyethylene

The effect of gamma radiation on the oxidation and wear resistance of ultra‐high molecular weight polyethylene (UHMWPE) has been extensively studied since these properties are critical for the longevity of UHMWPE components of total joint replacement prostheses. While gamma radiation increases wear resistance of UHMWPE, the free radical generated in the lamellar regions by radiation must be stabilized before oxidative degradation occurs as the polymer ages. Initially, post‐radiation melting conducted to quench free radicals but this treatment also decreases its mechanical properties. Recently, it has been replaced by incorporation of Vitamin E into UHMWPE to combat oxidative degradation. In this study, we assessed wear resistance of Vitamin E stabilized UHMWPE under abrasive wear conditions and oxidation resistance by shelf‐aging irradiated components for 2 years. Equilibrium swelling experiments showed that Vitamin E decreased crosslink density, which affected wear resistance, but oxidation resistance was better preserved with increasing concentration of Vitamin E. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44125.     

Determination of molecular weight and molecular sizes of polymers by high temperature gel permeation chromatography with a static and dynamic laser light scattering detector

Flow-mode static and dynamic laser light scattering (SLS/DLS) studies of polymers, including polystyrene, polyethylene, polypropylene and poly(dimethylsiloxane) (PDMS), in 1,2,4-trichlorobenzene (TCB) at 150 °C were performed on a high temperature gel permeation chromatography (GPC) coupled with a SLS/DLS detector. Both absolute molecular weight (M) and molecular sizes (radius of gyration, R_g and hydrodynamic radius, R_h) of polymers eluting from the GPC columns were obtained simultaneously. The conformation of different polymers in TCB at 150 °C were discussed according to the scaling relationships between R_g, R_h and M and the ρ-ratio (ρ=R_g/R_h). Flow-mode DLS results of PDMS were verified by batch-mode DLS study of the same sample. The presented technique was proved to be a convenient and quick method to study the shape and conformation of polymers in solution at high temperature. However, the flow-mode DLS was only applicable for high molecular weight polymers with a higher refractive index increment such as PDMS.     

Melt memory effects on recrystallization of polyamide 6 revealed by depolarized light scattering and small‐angle X‐ray scattering

Melt memory effects on recrystallization of polyamide 6 were studied in a length scale from nm to μm using small‐angle X‐ray scattering (SAXS) and depolarized light scattering (DPLS). The memory effects on recrystallization rate were discussed in terms of the incubation period before nucleation and the half time of the crystallization, which were measures of the nucleation rate and the growth rate, respectively. Both rates are almost independent of the annealing temperature of the melt in the remelting process for the short term annealing below ～ 3 min while they are slowed as the annealing temperature increases for the long term annealing, showing that the relaxation of melt memory takes very long even above the equilibrium melting temperature T. Extrapolating the incubation period to infinite annealing, time we found that it was very hard to attain the fully relaxed state in polyamide 6 even above the equilibrium melting temperature. This must be due to the strong hydrogen bonding in polyamide 6. We also discuss the memory effects on the final structure after recrystallization based on the SAXS and DPLS profiles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of β‐cyclodextrin for rapidly decolorizing the dye‐containing wastewaters by flocculation

To strengthen the role of polymer bridging during the flocculation process and thus raise the speed of decolorizing the dye‐containing wastewaters, β‐cyclodextrin–acrylamide–[2‐(Acryloyloxy)ethyl] trimethyl ammonium chloride copolymer (poly[AM(β‐CD)‐AETAC]) with relatively high intrinsic viscosity (84.3 mL g^?1) and cationicity (24.5%) was prepared by solution polymerization. The successful preparation of copolymer was demonstrated by FT‐IR and ¹H‐NMR characterizations. Its excellent decolorization performances as a new flocculant were evaluated with the C.I. reactive orange 5 (RO 5) and C.I. reactive blue 19 (RB 19) solutions using a jar test method. Both the nature of anionic dyes and the pH of dye solutions influence the decolorization effectiveness. For both the RB 19 and RO 5 solutions (0.10 g L^?1), it can be rapidly decolorized in a wide range of pH (2–7) and flocculant concentration (0.12–0.26 g L^?1). For the given dye/flocculant solution system, both charge neutralization and polymer bridging contribute to the decolorization mechanism. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39940.     

Quantitative relation between the relaxation time and the strain rate for polymeric solids under quasi‐static conditions

Relaxation time is an essential physical quantity reflecting the hysteresis of the microstructure of materials. To associate the relaxation time with the strain rate, the stress–strain curves of six types of polymers at low strain rate were normalized, and a nondimensional generalized Maxwell model incorporating strain‐rate‐dependent relaxation times was obtained by the internal variable theory of irreversible thermodynamics. The results indicate that the constitutive equation may capture well the normalized stress–strain behaviors that are not related to the strain rate. The ratio of the initial modulus to the secant modulus at the maximum stress was also found to not rely on the strain rate anymore. Furthermore, strain‐rate independence occurred only when the relaxation time was proportional to the time interval for stress from zero to the maximum stress. The relaxation time varied in a power law with the strain rate. The explicit relation is helpful for providing a concise and promising solution for predicting the quasi‐static mechanical response of viscoelastic solids. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44114.     

Characterization of poly (N‐vinyl formamide) by size exclusion chromatography–multiangle light scattering and asymmetric‐flow field‐flow fractionation–multiangle light scattering

The molar mass and the radius of gyration of three poly N‐vinyl formamide (polyNVF) synthesized in aqueous solution polymerization were characterized using two different fractionation techniques: size exclusion chromatography (SEC) and asymmetric‐flow field‐flow fractionation (AF4) coupled with a multiangle light scattering (MALS) and a refractive index (RI) detector. For the sake of comparison, the polymers were also characterized by MALS using the Zimm plot approach (no fractionation). The dn dc^?1 of the poly (N‐vinyl formamide) was measured (0.1564 mL g^?1) and it was found to be insensitive to the molar mass (in the range 150–450 kDa) and also to the eluents used (DDI water or mixed eluent DDI water/acetonitrile (80 : 20) at pH = 5.5). Interestingly, the concentrations of the samples injected in the SEC and AF4 should be different because concentrations in the range of 20–40 mg mL^?1 used for the AF4 caused overloading and anomalous elution in the SEC and hence misleading molar masses. At adequate concentrations in each fractionation equipment, the molar masses were in reasonable good agreement although AF4/MALS provided larger values than the other two techniques likely because samples were not filtered before injection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42434.     

Re‐entrant transition of aluminum‐crosslinked partially hydrolyzed polyacrylamide in a high salinity solvent by rheology and NMR

Linked polymer solution (LPS) is a nanoparticle polymer and designed by crosslinking a high molecular weight partially hydrolyzed polyacrylamide (HPAM) with aluminum (III). It has been applied in the oil industry to enhance oil recovery by improving sweep efficiency and by microscopic diversion in porous media. To achieve good propagation properties, aggregates formed by intermolecular crosslinking and gel formation should be avoided. To our knowledge, there is no established method to distinguish between intra‐ and intermolecular crosslinking for high molecular weight (>10 × 10⁶ Da), low concentration (<1000 ppm), polydisperse solutions of partially hydrolyzed polyacrylamides in high salinity solvents (5 wt % NaCl). The high salinity solvent is relevant to represent for formation water in many oil reservoirs. The main objective of the present study is to establish an experimental method for determining phase transition of LPS from monomeric coiled state to aggregated state in a high salinity solvent. No single experimental methods are conclusive and we have therefore applied a combinatorics approach including two‐dimensional NMR, dynamic rheology, and UV spectroscopy. The different techniques show similar trends, which allow overall interpretations of phase transitions to be made. The experimental results indicated that the LPS solution at high salinity solvent underwent a phase transition by chain re‐expansion, called reentrant transition. The transition point was observed at addition of 100 ppm of Al³⁺. Higher concentrations of Al³⁺ suppressed the rate of reentrant transition, most likely because of intramolecular crosslinking of HPAM chains by Al³⁺. Intermolecular crosslinking reaction was not observed at these conditions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43825.     

Creep characterization of vapor‐grown carbon nanofiber/vinyl ester nanocomposites using a response surface methodology

The effects of selected factors such as vapor‐grown carbon nanofiber (VGCNF) weight fraction, applied stress, and temperature on the viscoelastic responses (creep strain and creep compliance) of VGCNF/vinyl ester (VE) nanocomposites were studied using a central composite design (CCD). Nanocomposite test articles were fabricated by high‐shear mixing, casting, curing, and post curing in an open‐face mold under a nitrogen environment. Short‐term creep/creep recovery experiments were conducted at prescribed combinations of temperature (23.8–69.2°C), applied stress (30.2–49.8 MPa), and VGCNF weight fraction (0.00–1.00 parts of VGCNF per hundred parts of resin) determined from the CCD. Response surface models (RSMs) for predicting these viscoelastic responses were developed using the least squares method and an analysis of variance procedure. The response surface estimates indicate that increasing the VGCNF weight fraction marginally increases the creep resistance of the VGCNF/VE nanocomposite at low temperatures (i.e., 23.8–46.5°C). However, increasing the VGCNF weight fraction decreased the creep resistance of these nanocomposites for temperatures greater than 50°C. The latter response may be due to a decrease in the nanofiber‐to‐matrix adhesion as the temperature is increased. The RSMs for creep strain and creep compliance revealed the interactions between the VGCNF weight fraction, stress, and temperature on the creep behavior of thermoset polymer nanocomposites. The design of experiments approach is useful in revealing interactions between selected factors, and thus can facilitate the development of more physics‐based models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42162.     

Structure and properties of ultra‐high molecular weight bisphenol a polycarbonate synthesized by solid‐state polymerization in amorphous microlayers

The structure and properties of ultrahigh molecular weight polycarbonate synthesized by solid‐state polymerization in micro‐layers (SSP_m) are reported. A low molecular weight prepolymer derived from the melt transesterification of bisphenol A and diphenyl carbonate as a starting material was polymerized to highly amorphous and transparent polycarbonate of molecular weight larger than 300,000 g mol^?1 in the micro‐layers of thickness from 50 nm to 20 µm. It was observed that when the polymerization time in micro‐layers was extended beyond conventional reaction time, insoluble polymer fraction increased up to 95%. Through the analysis of both soluble and insoluble polymer fractions of the high molecular weight polycarbonate by ¹H NMR spectroscopy and pyrolysis‐gas chromatography mass spectrometry (Py‐GC/MS), branches and partially crosslinked structures have been identified. The thermal, mechanical and rheological properties of the ultra‐high molecular weight nonlinear polycarbonates synthesized in this study have been measured by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and rheometry. The nonlinear chain structures of the polymer have been found to affect the polymer's thermal stability, mechanical strength, shear thinning effect, and elastic properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41609.     

Cloud‐point measurements for salt + poly(ethylene glycol) + water systems by viscometry and laser beam scattering methods

The phase separation of salt + poly(ethylene glycol) + water systems was studied by cloud‐point measurements using viscometry and laser beam scattering methods. The Flory–Huggins model was applied to determinate the condition for salt‐induced liquid–liquid phase separation in the system. A temperature‐ and concentration‐dependent interaction parameter was employed to fit the phase diagrams for the systems. The temperature and concentration functionality of the interaction parameter was determined and used to predict cloud‐point curves for the systems. The cloud‐point curves were found to be in quantitative agreement with experimental data. Also, the effect of various salts on the measured cloud points was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1983–1990, 2003     

Water‐soluble allyl and diallyl camphor sulfonamides‐based polyacrylamide copolymers for enhanced oil recovery

The monomers N‐allyl camphor sulfonamide (CSAP) and N,N‐diallyl camphor sulfonamide (CSDAP) were copolymerized with acrylamide (AM), acrylic acid (AA) for EOR, respectively. The effect of the synthesis conditions on apparent viscosity was investigated, and the copolymers were characterized by Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance (¹H NMR), environmental scanning electron microscope (ESEM), and thermogravimetric analysis (TGA). Increasing mass ratio of diallyl CSDAP could lead to the water‐insoluble of copolymer, and competition of free radicals could make polymerization of AM/AA/CSDAP more difficult than AM/AA/CSAP. The thickening function and temperature resistance of two copolymers were remarkably improved in comparison with similar molecular weight partially hydrolyzed polyacrylamide (HPAM). In addition, the pronounced temperature resistance of the copolymers has been also demonstrated by temperature resistance test. It has also found that copolymers AM/AA/CSAP and AM/AA/CSDAP brine solutions could obtain significant enhanced oil recovery at 70°C suggesting their potential being applied in chemical enhanced oil recovery. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41238.     

Determination of molar mass and solution properties of cationic hydroxyethyl cellulose derivatives by multi‐angle laser light scattering with simultaneous refractive index detection

BACKGROUND: A complete understanding of the molar mass and solution properties of raw materials in bio/pharmaceutical products under bio‐application and natural conditions ensures process control, product performance and quality. Biopolymers including polymeric cationic hydroxyethyl cellulose derivatives (e.g. Polyquaterium‐10 or Polymer JR) have long been used in health care formulations including shampoos, lotions, eye drops and contact lens multi‐purpose solutions. Previously reported molar masses and conformation of Polymer JR were based on size exclusion chromatography‐related techniques, which required highly concentrated buffered salt solutions and organic solvent modifiers to prevent undesirable interactions, and did not represent the isotonic conditions in products and applications. RESULTS: This paper describes the characterization of Polymer JR in saline using a new approach that combines micro‐batch mode multi‐angle laser light scattering with simultaneous refractive index measurements (MB‐MALLS‐RI). Mass‐average molar mass, z‐average radius of gyration and second virial coefficient values in phosphate buffer saline (PBS) were obtained and are discussed in detail. CONCLUSION: The molar mass and solution properties of Polymer JR in PBS, with the same pH and ionic strength as most health care solution products, can be characterized using the MB‐MALLS‐RI technique. The approach is practical and can be widely used for the analysis of other cationic biopolymers. Copyright © 2009 Society of Chemical Industry     

Mechanical properties study of micro‐ and nano‐hydroxyapatite reinforced ultrahigh molecular weight polyethylene composites

This is a comparative study between ultrahigh molecular weight polyethylene (UHMWPE) reinforced with micro‐ and nano‐hydroxyapatite (HA) under different filler content. The micro‐ and nano‐HA/UHMWPE composites were prepared by hot‐pressing method, and then compression strength, ball indentation hardness, creep resistance, friction, and wear properties were investigated. To explore mechanisms of these properties, differential scanning calorimetry, infrared spectrum, wettability, and scanning electron microscopy with energy dispersive spectrometry analysis were carried out on the samples. The results demonstrated that UHMWPE reinforced with micro‐ and nano‐HA would improve the ball indentation hardness, compression strength, creep resistance, wettability, and wear behavior. The mechanical properties for both micro‐ and nano‐HA/UHMWPE composites were comparable with pure UHMWPE. The mechanical properties of nano‐HA/UHMWPE composites are better compared with micro‐HA/UHMWPE composites and pure UHMWPE. The optimum filler quantity of micro‐ and nano‐HA/UHMWPE composites is found to be at 15 wt % and 10 wt %, separately. The micro‐ and nano‐HA/UHMWPE composites exhibit a low friction coefficient and good wear resistance at this content. The worn surface of HA/UHMWPE composites shows the wear mechanisms changed from furrow and scratch to surface rupture and delamination when the weight percent of micro‐ and nano‐HA exceed 15 wt % and 10 wt %. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42869.     

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     

Crystallization behavior and foaming properties of polypropylene containing ultra‐high molecular weight polyethylene under supercritical carbondioxide

In this study, a systematic investigation on the nonisothermal crystallization kinetics of conversional polypropylene (PP) containing various amounts of ultra‐high molecular weight polyethylene (UHMWPE) was reported, and the effects of UHMWPE on crystallization behavior of these PP materials and their foaming properties were also presented. The kinetic studies revealed that the incorporation of UHMWPE into PP led to an increase in the crystallization temperature and temperature range during the crystallization process as well as the relative crystallinity. This behavior was attributed to a comprehensive effect of the nucleation and entanglement of the UHMWPE chains. The kinetic models based on Ozawa's and Mo's methods were used to analyze the nonisothermal crystallization behaviors. It was found that the latter succeeded in describing the nonisothermal crystallization behavior of the PP containing UHMWPE, while the former was not appropriate. The activation energy for the nonisothermal crystallization determined by Kissinger's method also indicated that the crystallization ability of PP was improved with the addition of UHMWPE. Owing to the modification of the crystallization kinetics of the PP materials by introduction of UHMWPE, the foaming properties (i.e., cell uniformity and expandability etc.) were improved significantly. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of the carboxyl‐ended hyperbranched polyester/platinum complex molecular weight on hydrosilylation activity and self‐assembled morphology

Research on platinum catalysts with high activity and long life for hydrosilylation has attracted a great deal of interest because of the increasing price of platinum metal. In this study, we examined the effect of the molecular weight of carboxyl‐ended hyperbranched polyester/platinum complexes (HTD‐n–Pt's, where n = 1, 2, 3, or 4) on hydrosilylation activity and self‐assembled morphology. Relevant parameters tuning the morphology of self‐assemblies, such as the temperature, time, concentration, and relative humidity, were examined. All of the HTD‐n–Pt's with various molecular weights had much higher hydrosilylation activities than did the conventional homogeneous Speier's catalyst, and the HTD‐n–Pt could be self‐assembled into ordered two‐dimensional treelike structures with a fractal dimension ranging from 1.48 to 1.83; this indicated perfect fractal properties. With the increase of the HTD‐n–Pt molecular weight, the size of the self‐assembled treelike structures and the catalytic activity increased first and then decreased. The self‐assembly mechanism was speculated and analyzed by dynamic light scattering, X‐ray photoelectron spectroscopy, X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy; these suggested good agreement with the diffusion‐limited aggregation theory of particles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41416.