Shear rheological properties of acrylic copolymers and terpolymers suitable for potentially melt processable carbon fiber precursors

In an effort to generate melt processable polyacrylonitrile (PAN) precursor fibers suitable for conversion to carbon fibers, an acrylonitrile/methyl acrylate (AN/MA) copolymer and two acrylonitrile/methyl acrylate/acryloyl benzophenone (AN/MA/ABP) terpolymers were synthesized at molar ratios of 85/15 and 85/14/1, respectively. The termonomer (ABP) was incorporated to accelerate crosslinking via UV irradiation, which serves to prevent relaxation of orientation and flow as the temperature of the fiber is raised during thermooxidative stabilization. Two molecular weights of the terpolymer and one molecular weight of the copolymer were studied to determine the effect of the termonomer, and the effect of molecular weight (MW), on the steady shear viscosity (η) and magnitude of the complex viscosity (η*). A higher rate of increase of η as a function of time was observed for the high MW terpolymer relative to that of the copolymer over the temperature range used. Using a temperature sweep and monitoring levels of η*, a minimum was observed at lower temperatures for both terpolymers. These results suggest that copolymerization with ABP significantly increased the thermally induced kinetics of crosslinking. Comparison of the η and η* data for the low and high MW terpolymers suggested that molecular weight also significantly reduced the melt stability (increased the kinetics of crosslinking). A chemorhelogical correlation was then used to quantify the effects of the termonomer and of molecular weight on the kinetics of crosslinking of the AN terpolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2856–2865, 2004     

Fluorinated phenylethynyl-terminated imide oligomers with reduced melt viscosity and enhanced melt stability

Two novel fluorinated phenyethynyl-contained endcapping agents, 4-(3-trifluoromethyl-1-phenylethynyl)phthalic anhydride (3F-PEPA) and 4-(3,5-bistrifluoromethyl-1-phenylethynyl)phthalic anhydride (6F-PEPA) were synthesized, which were employed to synthesize two fluorinated model compounds, N-phenyl-4(3-trifluoromethyl)-phenylethynylphthalimide (3F-M) and N-phenyl-4(3,5-bitrifluoromethyl)-phenylethynyl phthalimide (6F-M). The thermal cure kinetics of 3F-M and 6F-M were analyzed using DSC and compared to the unfluorinated derivative, N-phenyl-4-phenylethynylphthalimide (PEPA-M). The thermal cure temperatures of 3F-M and 6F-M were 399 and 412 °C, which were 22 and 35 °C higher than that of PEPA-M, respectively. The thermal cure kinetics of 3F-M and 6F-M best fit a first-order rate law, although 3F-M and 6F-M reacted slower than PEPA-M. However, the exothermic enthalpy of 3F-M and 6F-M were only half of PEPA-M. Based on the model compounds study, a series of fluorinated phenylethynyl-terminated imide oligomers (F-PETIs) with different calculated molecular weights (Calc'd M_n) were synthesized by thermal polycondensation of 2,3,3′,4′-biphenyltetracarboxylic acid dianhydride (a-BPDA) and 3,4′-oxydianiline (3,4′-ODA) using 3F-PEPA or 6F-PEPA as the endcapping agent. The substituent effects of the trifluoromethyl (−CF₃) groups on the thermal cure behavior and melt processability of F-PETIs were systematically investigated. Experimental results reveal that the melt processability of F-PETI was apparently improved by the reduced resin melt viscosities and the enhanced melt stability due to the incorporation of the −CF₃ groups in the imide backbone. All of those F-PETIs exhibit outstanding thermal and mechanical properties.     

Poly (acrylonitrile - co -1-vinylimidazole): A new melt processable carbon fiber precursor

Acrylonitrile/1-vinylimidazole (AN/VIM) copolymers containing various mol% of VIM were synthesized by free radical solution polymerization. The copolymers were characterized by Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy, ¹H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Char yields of the copolymers were 40-48% as determined by thermogravimetric analysis (TGA) while gel fractions were found to be 90-99% depending upon the composition, temperature and time. The complex viscosity of the precursor copolymers was measured as a function of composition and temperature. 82/18 mol% of AN/VIM copolymer based carbon fiber precursor was successfully processed by solvent-free melt spinning at 192 °C and the melt-spun fiber was characterized by DSC, ATR-IR, and X-ray Diffraction (XRD).     

The characterization of rheological properties of melt grafting polypropylene for foaming

Large enhancements of the melt strength of polypropylene (PP) were achieved by the introduction of specific unsaturated linear polyester (ULP) branches using melt grafting. The transient torque curves and optical rheology microscope images indicated that branching reactions took place and the ULP had been grafted onto the PP backbone. Shear rheological behaviors of three kinds of PP were investigated using rotational rheometer under dynamic shear mode with periodic shear rate. These PP samples are foamable PP (FPP) with sparse branches obtained by grafting ULP, commercial high melt strength PP (HMS PP) for foaming and conventional linear PP (EPS). It was found that the rheological properties of FPP, the HMS PP, were distinctly different from those of conventional PP. Storage modulus, steady state compliance and zero shear viscosity increased in comparison with EPS, while shear viscosity decreased. This result implied the presence of branching structures that was not revealed in conventional PP. In melt flow measurements, extrusion swell that was a prominent behavior of branching PP was observed also for FPP and PF. Compared to linear PP, FPP and PF showed distinct sag-resistant property and lower melt flow index. On the other hand, to estimate the extent of branching, a detailed method was applied using the obtained zero shear viscosity. The result showed that FPP was grafted by sparse ULP. From these results, it was found that FPP showed obvious enhancements in rheological behaviors similar to PF, although its melt strength was lower than that of PF due to the presence of shorter branching chains grafted on the backbone of FPP.     

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.     

Synthesis and characterization of acrylonitrile methyl acrylate statistical copolymers as melt processable carbon fiber precursors

Statistical (random) copolymers of acrylonitrile (AN) and methyl acrylate (MA) have been synthesized by free radical homogeneous (solution) and heterogeneous (suspension) methods. Selected compositions can be fabricated by environment friendly, solvent-free melt spinning and are of interest as precursors for carbon fibers. The dynamic and steady state melt viscosities of these copolymers were studied as a function of molecular weight and copolymer composition. Melt processability at 200–220 °C depends on the copolymer composition, and also on the molecular weight, which was controlled by chain transfer agent concentration and reaction temperature. Copolymers of controlled molecular weight containing 10 or more mol[percnt] of methyl acrylate show good melt processability, which can be further enhanced by stabilizers. This thermoplastic behavior is supported by a significant increase in temperature by the cyclization exotherm. Thermal analysis (differential scanning calorimetry, dynamic mechanical analysis) further illustrates that the comonomers retarded the cyclization, which permits thermoplastic processing.     

Dynamic mechanical and melt rheological properties of sulfonated poly(butylene succinate) ionomers

A series of poly(butylene succinate) ionomers (PBSi) containing 5-sodium sulfoisophthalate units were prepared by bulk polymerization of succinic acid and 1,4-butanediol in the presence of dimethyl 5-sulfoisophthalate sodium salt (DMSI) up to 5 mol% of diacid monomer. Conspicuous variation of the storage modulus for PBSi was observed, depending on the content of DMSI. The increasing rate of cluster T_g was lower compared to those of amorphous polymer-based ionomers. These results were probably due to the lower clustering ability of semi-crystalline PBSi as compared with amorphous-based ionomers. Non-contact atomic force microscopy confirmed that the size of PBSi-3 clusters was about 40∼50 nm, demonstrating that the clusters were aggregated. Melt rheological analysis was carried out to investigate the effects of ionic groups on the rheological properties as a function of temperature or shear force in the molten state. The melt viscosities of PBSi showed higher values than the parent PBS up to about 190 °C, while with further increasing temperature a falling inflection region of melt viscosity was observed. It was suggested that the relaxation of PBSi chains was due to the thermal dissociation of ionic aggregates.     

Dichotomous behavior of polymer melts in isothermal melt spinning

Isothermal melt spinning experiments have been conducted using two polyethylene melts of low density (LDPE) and high density (HDPE) to produce steady state spinline profiles. The data revealed the threadline extensional viscosity exhibiting a contrasting picture : extension thickening behavior for LDPE and extension thinning one for HDPE. A White-Metzner model having a strain rate-dependent relaxation time was then found to be able to simulate this dichotomy in melt spinning fairly well: the fluids whose relaxation times have smaller strain rate-dependence can fit LDPE data with extension thickening extensional viscosity whereas the fluids whose relaxation times have larger strain rate-dependence can fit HDPE data with extension thinning extensional viscosity. This dichotomous nature of viscoelastic fluids is also believed to be able to explain other similar contrasting phenomena exhibited by polymer melts, such as vortex/no vortex in entry flows, cohesive/ductile fracture modes in extension, and more/less stable draw resonance than Newtonian fluids.     

Mathematical modeling and the estimation of parameters for the melt viscosity of polyamides

Capillary rheometry data of a range of commercial polyamide engineering materials was obtained from a mould-flow analysis material database, from which melt viscosity data was obtained at different temperatures, which made comparison of the viscosities difficult. In an attempt to make a reasonable comparison between the melt viscosities of the various polyamide materials at different temperatures, it was necessary to obtain the mathematical functions which describe the relationships between: (i) the melt viscosity and the shear rate, (ii) the melt viscosity and temperature and (iii) the melt viscosity and the combined effect of the shear rate and temperature of each of the polyamides studied. Therefore, melt viscosity was modelled as a function of shear rate at the three temperatures (275°C, 295°C and 315°C), at which the viscosities were determined. The function obtained represented smoothed versions of the experimental data, eliminating the experimental noise and enabling the generation of melt viscosity data at the six different shear rates of the original data. It was established that the melt viscosity as a function of shear rate at constant temperature, in the shear rate range 500-700 s m 1 , is incorrectly described by the Ostwald-de-Waele's model, \eta_{\rm T}={\rm f}({\dot \gamma})={\rm K}({\dot \gamma})^{({\rm n}-1)} , while the melt viscosity of the polyamides studied, as a function of temperature, is correctly described by the model \eta_{\dot \gamma}={\rm g}{(\rm T)}={\rm Pe}^{\left (\rm {QT/R}\right )} . But the response-surface melt viscosity is effectively described as a function of both shear rate and temperature by the model: \eta=\vert {\dot \gamma}\vert^{(\rm n-1)}{\rm Ae}^{(\rm ET/R)} . The parameters A, E and n are highly interrelated as they all influence the average melt viscosity. All are temperature sensitive and also, to some degree, shear sensitive.     

Facile synthesis of processable aromatic polyamides containing thioether units

Aromatic polyamides containing thioether units were synthesized by interfacial polycondensation of 4,4′‐thiodibenzoyl chloride (or 4,4′‐bis(4‐chloroformylphenylthio)benzene) with aromatic diamines containing a nitrile unit. Their structure was established using ¹H NMR and Fourier transform infrared spectroscopy. The inherent viscosities of the polyamides prepared with optimum synthesis conditions were in the range 0.71–0.84 dL g^?1. These polyamides showed excellent thermal properties with glass transition temperatures of 210.5–219.6 °C, melting temperatures of 313.8–315.0 °C and initial degradation temperatures of 440–459 °C. They could be processed by melting due to their relatively wide processing window. Their tensile strengths were 71.3–79.1 MPa, water absorption was 0.17–0.22 wt%, and melt flowability was in the range 64.5 to 315.2 Pa s and 68.5 to 422.3 Pa s at different shear rates. At the same time, they were soluble in aprotic solvents such as N‐methyl‐2‐pyrrolidone, dimethylformamide and dimethylsulfoxide. The results suggest that these aromatic polyamides containing thioether units represent a promising type of heat‐resistant and processable engineering plastic. © 2012 Society of Chemical Industry     

Processing and properties of injection molded thermoplastic composites reinforced with melt processable glasses

This work was concerned with evaluating the properties of injection molded composites comprising polyetherimide (PEI) and polyetheretherketone (PEEK) reinforced with various lower T_g melt processable phosphate glasses. Composites were produced utilizing a variety of glass and resin combinations in order to ascertain the effects of factors such as glass concentration and viscosity of the components on the mechanical properties of the composite blends. Changes in the rheological and interfacial properties of the blends obtained by varying the resins and phosphate glasses used during processing resulted in a variety of reinforcing morphologies consisting of glass beads, ribbons, and an interpenetrating network structure. The large variations in the glass phase morphologies obtained during injection molding led to composites that displayed a wide range of properties. Generally, it was found that the use of resin/glass combinations that minimized the viscosity difference between the components resulted in composites displaying the best overall mechanical properties. The stiffness of the composites was found to increase with glass concentration with loadings up to 45 vol% glass, leading to moduli 3‐4 times greater than those of the neat resins. While the addition of the phosphate glasses produced significant enhancements in the stiffness of the composite blends, the strength often fell to values 2‐3 times lower than those of the neat resins.     

Observation of melt fracture of polypropylene resins in capillary flow

Melt fracture, shear viscosity, extensional viscosity, and die swell of two polypropylene resins were studied using a capillary rheometer. A modified Bagley plot with consideration of pressure effects on melt viscosity and end effect was used. From the true wall shear stress the shear viscosity was calculated. Extensional viscosity was calculated from the end effect. Both shear and extensional viscosities of different molecular weights and temperatures correlated well under the time-temperature Williams-Landel-Ferry (WLF) superposition. Die swell increased when shear stress increased, and was higher for shorter dies at a given shear rate. When shear rates increased the extrudate staged from smooth to gross melt fracture with regular patterns (spurt), and then turned into irregular shapes. In the regular stage the wavelength of extrudates was measured, and corresponding frequency was calculated. The frequency increased when molecular weight decreased and when melt temperature increased. The shift factor based on shear viscosity also brought frequency data of different molecular weights and temperatures into master curves. The frequency decreased slightly when die lengths increased from L/R=10 to 60. A small maximum was observed when shear rates increased.     

PVA/TPU共混材料热塑加工性能及相容性的研究

采用热塑加工方法制备了聚乙烯醇/热塑性聚氨酯(PVA/TPU)共混材料,系统研究了共混材料的热塑加工性能、相容性及力学性能。结果表明:TPU的引入对共混材料的熔点影响不大,但其与PVA间的氢键作用可屏蔽PVA的羟基,较大幅度地提高了PVA初始热分解温度,获得更宽的热塑加工窗口;引入适量的TPU还可降低共混材料的熔体黏度,改善材料的热塑加工性能,另外,还可获得良好的材料相容性;随着TPU用量的增加,共混材料的拉伸强度先增后降,并在TPU用量为50 phr时达到最大值。     

Properties of melt processable PTFE/PEEK blends: The effect of reactive compatibilization using electron beam irradiated melt processable PTFE

For the first time, blends of melt processable polytetrafluoroethylene (MP PTFE) with polyetheretherketone (PEEK) in the MP PTFE/PEEK ratio of 100/0, 80/20, 50/50, 20/80, and 0/100 w/w were prepared and characterized. MP PTFE/PEEK blends are attractive materials due to the combination of low coefficient of friction and universal chemical resistance of MP PTFE with good wear resistance and mechanical strength of PEEK while maintaining high thermal stability of both. Miscibility, phase morphology, and mechanical properties of the new MP PTFE/PEEK blends were investigated. To improve their end‐use properties, an attempt of reactive compounding with the electron beam irradiated MP PTFE (e‐beam MP PTFE) was made. The reactive compounding was done in two steps, that is, the preparation of a masterbatch (MB) consisting of e‐beam MP PTFE/PEEK (50/50 w/w) and subsequent melt blending of MP PTFE/PEEK with varying concentrations of MB. The e‐beam irradiation of MP PTFE carried out in air atmosphere and at room temperature with a dose of 50 kGy results in its chain scission associated with formation of ? COF and ? COOH functional groups. Such modified MP PTFE can be used to compatibilize MP PTFE/PEEK blends. Reactive compatibilized blends exhibit improved phase morphology and mechanical properties. Especially for MP PTFE/PEEK 50/50 blends, a great improvement of almost 250% in strain at break, 40% in stress at break, and more than 600% in toughness was achieved. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamic melt properties of polymer blends

The dynamic mechanical properties of blends of polymer melts were measured using the orthogonal rheometer. Two-phase blends, polyethylene-polystyrene, polyethylene-poly-(methylmethacrylate), and polystyrene-polymethylmethacrylate, were studied. The in-phase and out-of-phase moduli were measured over the range of composition and at frequencies between 10^?4 and 10 revolutions/sec. The out-of-phase modulus increases in a monotonic manner with composition. The in-phase modulus, however, shows a maximum with composition in two cases. Examination of the relaxation spectra of these blends shows that when no maximum occurs it can be written as an additive function of the spectra of the components. In the case where a maximum is observed in the modulus the measured spectrum of the blend is shifted in frequency relative to the calculated one. This is tentatively attributed to slight interpretation and solubility of one phase in the other in these cases.     

Rheological behavior of polypropylene/layered silicate nanocomposites prepared by melt compounding in shear and elongational flows

Melt rheology and processability of exfoliated polypropylene (PP)/layered silicate nanocomposites were investigated. The nanocomposites were prepared by melt compounding process in the presence or absence of a PP‐based maleic anhydride compatibilizer. PP/layered silicate nanocomposites showed typical rheological properties of exfoliated nanocomposites such as nonterminal solid‐like plateau behavior at low frequency region in oscillatory shear flow, higher steady shear viscosity at low shear rate region, and outstanding strain hardening behavior in uniaxial elongational flow. The melt processability of exfoliated PP/layered silicate nanocomposites was significantly improved due to good dispersion of layered silicates and increased molecular interaction between the PP matrix and the layered silicate organoclay. Small‐angle X‐ray scattering and transmission electron microscopy results revealed that the layered silicate organoclay was exfoliated and good interaction between PP matrix and organoclay was achieved by using the PP‐g‐MAH compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3506–3515, 2007     

Estimation of the melt rheology of polymer waste from melt flow index

The need for recycling of polymeric waste has been well recogmized as a result of the escalating prices of the petrochemical feedstocks and the growing awareness to curtail solid waste that causes environmental pollution. During processing, the molecular weight of the polymer is reduced due to thermal and shear degradation. Since the melt rheology of the processed material is sensitive to the changes in molecular structure, knowledge of the complete flow curve depicting the variation of melt viscosity with shear rate at processing temperatures is a useful tool for assessing the reprocessibility of waste material and for specifying the conditions of reprocessing. In the present paper, an effective method is proposed to generate the melt flow curves of polymer waste from knowledge of its melt flow index. The method makes use of a master curve that can be obtained by plotting the available viscosity data in terms of modified functions based on the melt flow index. The master curves characteristic of the particular generic resin type are presented for low-density polyethylene, polypropylene and polystyrene.     

Mechanical properties of PAN-based gel electrolytes: small-amplitude oscillatory shear study

Abstract

Polymer electrolytes with ionic conductivities on the order of mS cm^-1 at room temperature were prepared from the gelification of LiClO₄ /ethylene carbonate–propylene carbonate (EC–PC) solutions into a poly(acrylonitrile) (PAN) matrix. Oscillating rheological experiments were performed on gels prepared at different solvent/salt molar ratios in order to investigate their mechanical properties. Temperature sweep tests (25–120°C) showed changes in the rheological behaviour that was related to structural transitions. A strong–weak gel transition takes place at about 80°C, independent of salt concentration hence assignable only to the polymeric matrix. This transition is completely reversible during cooling ramps and represents a necessary mechanical property from a processing standpoint. A gel–sol transition was observed at ca. 110°C where both viscoelastic moduli reduce themselves by a factor 100, reporting the formation of a fluid system with G''>G'.     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

Preparation and characterization of new melt compounded copolyamide nanocomposites

In this work new copolyamide-layered silicate nanocomposites were prepared by melt compounding using a commercial polyamide 6-based copolymer, with a partially aromatic structure, as thermoplastic matrix. This copolyamide, having a lower melting point and improved mechanical and barrier properties respect to the homopolymer, appears an interesting material for producing nanocomposite packaging films. Hybrids with different organoclay loadings were produced by a twin-screw extruder using different extrusion rates, in order to point out the effects of both processing conditions and hybrid composition on morphology (silicate dispersion and exfoliation, orientation, matrix crystallinity) of nanocomposites. All melt-intercalated samples were submitted to structural (TEM and XRD), thermal and dynamic mechanical measurements. The performed analyses have evidenced that all hybrids exhibit mixed intercalated/exfoliated morphology and that the extent of exfoliation increases with both clay amount and extrusion rate used. Moreover, it was pointed out that the silicate nano-scale dispersion significantly affects the crystalline morphology of copolyamide matrix, stabilizing the γ-crystal phase, and the dynamic mechanical response of the hybrids, whose storage and loss moduli values result sensibly higher than those corresponding to the neat matrix.