Rheological Characterization of Metalized and Non‐Metalized Ethanol Gel Propellants

The gellation of metalized and non‐metalized ethanol with a methylcellulose gelling agent and its effect on the rheological properties (flow and dynamic study) of these gels is reported herein. The rheological study shows that increasing the shear rate reduces the apparent viscosity for a given yield stress (for a shear rate range of 1 to 12 s⁻¹) for both shear rate ranges (1 to 12 and 1 to 1000 s⁻¹) covered in present experiment. The gellant and metal particle concentrations significantly influence the gel apparent viscosity. Distinct changes in thixotropic behavior were observed, while decreasing the concentration of MC gellant and Al metal particles in the ethanol gels. The dynamic study showed that all of the linear viscoelastic regions (LVE) of the gel samples were independent of strain percentage (1 to 10). The G′ values depended on the frequency and exceeded the G′′ values, which indicated a gel‐like highly structured material. The tanδ values showed that all of the ethanol gels were elastic and weak physical gels with a high degree of cross‐linking.     

Determining the gel point of an epoxy–hexaanhydro‐4‐methylphthalic anhydride (MHHPA) system

The DEBGA–MHHPA epoxy system has found increasing applications in microelectronics packaging for which the ability to understand and model the cure kinetics mechanism accurately is crucial. The present article reports on the work done to elucidate accurate knowledge of the gel point by rheological methods. To determine the gel point using the G′–G″ crossover method was found not to be accurate, and the gel point obtained by this method was found to be frequency‐dependent. Using the point where tgδ was found independent of the frequency can accurately define the gel point at different temperatures. At the gel point determined by this method, G′ and G″ were found to follow the same power law, demonstrating the accuracy of the method in determining the gel point. The scaling exponent obtained was 0.75–0.79. The activation energy for the cure reaction of the system was determined to be 75.1 kJ/mol by the obtained gel times at different temperatures. The steady‐shear rheology test was also used to observe the viscosity change at the gel point. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1248–1256, 2000     

超高分子量聚乙烯凝胶的流变行为

采用旋转流变仪研究了超高分子量聚乙烯(UHMWPE)凝胶的流变行为。通过动态应变扫描测定了UHMWPE凝胶的线性黏弹区;通过动态温度扫描、动态频率扫描和稳态速率扫描研究了温度、浓度、剪切速率对凝胶流变行为的影响。结果表明,浓度为2%~22%的UHMWPE凝胶的线性黏弹区对应的应变下限为2%,上限为40%,且温度对凝胶线性黏弹区的影响较大;浓度为6%的UHMWPE凝胶,在180℃时,弹性模量最大,凝胶内部的黏结性最强;UHMWPE凝胶熔体的黏度随扫描频率、剪切速率的升高而降低,呈现明显的剪切变稀行为,属于假塑性流体;剪切速率较高时,UHMWPE凝胶的黏度对温度的变化更敏感。     

Rheological behavior of ultrahigh molecular weight polyethylene semidilute solutions. II. Effect of aluminium stearate

The effect of aluminium stearate on the rheological behavior of ultra-high molecular weight polyethylene (UHMWPE) semidilute solutions with paraffin oil as the solvent has been investigated. Adding aluminium stearate to paraffin oil can prevent the spinning solution from adhering to the pipe or screw, greatly improving the flow behavior of UHMWPE solutions. The geometric sizes of spinnerette hole, such as length–diameter ratio L/D and entrance angle of a capillary, also affect the flow behavior of the spinning solution. The calculated first normal stress difference σ₁₁ ? σ₂₂ and the Bagley-end correction e from experimental data show that the elastic effect on spinning solutions in flow is quite large, although the shear rate is below 20 s^?1.     

Spinning and drawing properties of ultrahigh‐molecular‐weight polyethylene fibers prepared at varying concentrations and temperatures

The concentrations and temperatures of ultrahigh‐molecular‐weight polyethylene (UHMWPE) gel solutions exhibited a significant influence on their rheological and spinning properties. The shear viscosities of UHMWPE solutions increased consistently with increasing concentrations at a constant temperature above 80°C. Tremendously high shear viscosities of UHMWPE gel solutions were found as the temperatures reached 120–140°C, at which their shear viscosity values approached the maximum. The spinnable solutions are those gel solutions with optimum shear viscosities and relatively good homogeneity in nature. Moreover, the gel solution concentrations and spinning temperatures exhibited a significant influence on the drawability and microstructure of the as‐spun fibers. At each spinning temperature, the achievable draw ratios obtained for as‐spun fibers prepared near the optimum concentration are significantly higher than those of as‐spun fibers prepared at other concentrations. The critical draw ratio of the as‐spun fiber prepared at the optimum concentration approached a maximum value, as the spinning temperature reached the optimum value of 150°C. Further investigations indicated that the best orientation of the precursors of shish‐kebab‐like entities, birefringence, crystallinity, thermal and tensile properties were always accompanied with the as‐spun fiber prepared at the optimum concentration and temperature. Similar to those found for the as‐spun fibers, the birefringence and tensile properties of the draw fibers prepared at the optimum condition were always higher than those of drawn fibers prepared at other conditions but stretched to the same draw ratio. Possible mechanisms accounting for these interesting phenomena are proposed.     

Rheological aspects of microbial hyaluronic acid

The rheological properties of the hyaluronic acid (HA) produced by the cultivation of Streptococcus zooepidemicus ATCC 39920 in synthetic medium at constant pH of 7.0 were determined. Relevant characteristics of the biopolymer as its pureness related to proteins (0.44 mg of protein per gram of HA) and its average molar weight (4.0 × 10⁶ Da) were also determined. Experimental data in steady shear (flow curves) have been correlated with the Cross model, which described the apparent viscosity shear rate data well mainly at concentrations higher than 50 mg mL^?1.The concentration dependence of specific viscosity showed two linear regimes that intercept at critical overlap concentration (c*) equal to 4 mg mL^?1. The storage (G′) and loss (G″) moduli increasing along the HA concentration and estimates out of the studied range indicate that a crossover frequency decreased with the increasing concentration of HA. The high concentration dependence of G′ as well as the deviations of the Cox‐Merz rule for most of the HA concentrations indicate the hyperentangled properties for the HA chains, which could be visualized through atomic force microscopy images even at low concentrations as 0.01 mg mL^?1. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

高浓度超高相对分子质量聚乙烯冻胶流变行为的研究

应用Rosand RH7D型双料筒毛细管流变仪,研究了以白油为溶剂的高浓度超高相对分子质量聚乙烯(UHMWPE)冻胶的流变特性,以及冻胶浓度、温度对高浓度冻胶的流变曲线、非牛顿指数和结构黏度指数的影响。结果表明:高浓度UHMWPE冻胶属于宾汉流体,不同浓度的UHMWPE冻胶非牛顿指数随温度的升高先增大后减小,结构黏度指数随UHMWPE冻胶浓度及温度的增高而减小。     

Camphene/polystyrene solutions: A rheological approach for material processing industry

Rheological properties of polymer–camphene solutions are very relevant as they affect their stability, and they have many implications in operation costs. This work elucidates the rheological properties of polystyrene (PS–camphene) solutions with industrial applications. Unfortunately, the assessment of the very low shear viscosities of camphene-based materials (below 0.005 Pa s) is still a challenge with commercial rheometers. Flow curves, stress growth tests, and small amplitude oscillatory shear (SAOS) measurements were carried out as a function of PS concentration (0, 2.5, 5.0, 10, and 20 wt % PS) to understand the rheological behavior of these systems. Results indicate that liquid camphene has a shear-thinning behavior (flow index = 0.99) when the increase of polymer concentration involves changes in the structure of these systems (flow index = 0.10 for 20 wt % PS). An increase in PS concentration leads to a forwarding in the shear-thinning zone, and the Newtonian region (from ∼1 s⁻¹, for 0 wt % PS, to 10⁻³ s⁻¹ for 20 wt % PS). Eventually, these results evidence the high dependence of η_∞ on PS concentration (from ∼1.16 ± 0.01 Pa s, for 0 wt % PS, to 631.5 ± 0.2 Pa s for 20 wt % PS). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47953.     

Lower Newtonian viscosities of polystyrene

A falling coaxial cylinder viscometer was used to measure the melt flow behaviour of a commercial polystyrene with Mw 260,000. The shear stress region extended down to 0.6 × 10⁴ dynes/cm² and shear rates were as low as 3 × 10^?2 sec^?1 at 186°C. The shear rate-shear stress plots were linear at low shear stresses with slopes (differential viscosities) of 3.3 × 10⁵ poises at total shear less than 120 units and decreasing differential viscosity with higher total shear. The flow curves at relatively low total shear were initially dilatant and became pseudoplastic with increasing shear stress. The inflection point represents a Newtonian apparent viscosity, which agrees fairly well with literature values for polystyrenes of the same Mw. Newtonian apparent viscosity is characteristic of a point value of shear stress and shear rate and is not necessarily a plateau region. Observation of a Newtonian region with decreasing shear stress or shear rate does not prove that this flow regime persists unchanged to zero values of the experimental parameter. The existence and magnitude of the Newtonian apparent viscosity reflects shear history of the polymer as well as its constitution and molecular weight distribution.     

Flow behavior of polyacrylamide solution. III. Mathematical treatment

The flow behavior of polyacrylamide solutions was systematically determined over a wide range of temperatures (20–50°C) and concentrations (20–50 ppm) by using a coaxial cylinder viscometer. The results indicated that the rheological behavior of low-concentration polyacrylamide solution behaves similar to non-Newtonian fluids at all these concentrations. The effect of temperature on the consistency coefficient and flow behavior index of polyacrylamide solution of the different concentrations followed an Arrhenius-type relationship. Moreover, the effect of concentration on consistency coefficient and flow behavior index followed an exponential-law relationship at the temperatures used. The rheological constants for the Arrhenius and exponential-law models were determined. The combined effect of temperature and concentration on the coefficient of dynamic shear stress can be represented by a single equation: shear stress = 2.446 × 10⁻⁷exp(0.0639C + 3613/RT)(shear rate)^{2.337 exp(−0.00707C−245/RT)}. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2784–2789, 2001     

Investigation of the ultradrawing properties of gel spun fibers of ultra‐high molecular weight polyethylene/carbon nanotube blends

The carbon nanotubes (CNTs) contents, ultrahigh‐molecular‐weight polyethylene (UHMWPE) concentrations and temperatures of UHMWPE, and CNTs added gel solutions exhibited significant influence on their rheological and spinning properties and the drawability of the corresponding UHMWPE/CNTs as‐prepared fibers. Tremendously high shear viscosities (ηs) of UHMWPE gel solutions were found as the temperatures reached 140°C, at which their ηs values approached the maximum. After adding CNTs, the ηs values of UHMWPE/CNTs gel solutions increase significantly and reach a maximum value as the CNTs contents increase up to a specific value. At each spinning temperature, the achievable draw ratios obtained for UHMWPE as‐prepared fibers prepared near the optimum concentration are significantly higher than those of UHMWPE as‐prepared fibers prepared at other concentrations. After addition of CNTs, the achievable draw ratios of UHMWPE/CNTs as‐prepared fibers prepared near the optimum concentration improve consistently and reach a maximum value as their CNTs contents increase up to an optimum value. To understand these interesting drawing properties of the UHMWPE and UHMWPE/CNTs as‐prepared fibers, the birefringence, thermal, morphological, and tensile properties of the as‐prepared and drawn fibers were investigated. Possible mechanisms accounting for these interesting properties are proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

High shear strain rate rheometry of polymer melts

The rheology of a range of polymer melts has been measured at strain rates above those attained during conventional rheometry using an instrumented injection molding machine. Deviations from shear thinning behavior were observed at high rates, and previously unreported shear thickening behavior occurred for some of the polymers examined. Measured pressure and volumetric throughputs were used to calculate shear and extensional viscosity at wall shear strain rates up to 10⁷ s^?1. Parallel plate rheometry and twin bore capillary rheometry were used to provide comparative rheological data at low and medium shear strain rates, respectively. Commercial grades of polyethylene, polypropylene, polystyrene, and PMMA were studied. Measured shear viscosity was found to follow Newtonian behavior at low rates and shear thinning power law behavior at intermediate strain rates. At shear strain rates approaching or above 10⁶ s^?1, shear viscosity reached a rate‐independent plateau, and in some cases shear thickened with further increase in strain rate. A relationship between the measured high strain rate rheological behavior and molecular structure was noted, with polymers containing larger side groups reaching the rate‐independent plateau at lower strain rates than those with simpler structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The Rheology of Peat/Solvent Slurries

Slurries of finely milled Irish peat in Shell White Spirit (100F) were prepared and their rheological behaviour was evaluated in terms of shear rate, solids concentration, moisture content and particle size distribution of the solids. The moisture content of the peat was found to be of crucial significance in determining both the effective solids concentration and the stability of the suspensions. The viscosity of slurries composed of 7% moisture peat solids were almost independent of solids concentration and displayed Newtonian rheological behaviour, with a viscosity of approximately 0·012 N s m⁻². The viscosity of the suspending medium was 1·006×10⁻³ N s m⁻² at 20±1°C. The viscosity of the slurries composed of 55% moisture peat solids was observed to rise sharply, up to about 0·10 N s m⁻² with solids concentration. The shear rate dependence of these suspensions was more complex and their flow characteristics were evaluated in terms of empirical non-Newtonian models. It proved difficult to confidently distinguish between the Bingham Plastic and Casson models as each gave best fit regression curves which were almost identical. Particle size distribution analysis of the suspensions indicates the formation of peat aggregates in the 55% moisture samples which exhibited more rapid settling of the solid. © 1997 SCI     

Rheology of low nematic transition temperature thermotropic liquid crystalline copolyester HBA/HQ/SA

The rheology of a liquid crystalline copolyester of hydroxybenzoic acid, hydroquinone, and sebacic acid (HBA/HQ/SA copolyester) was studied on both a rotational and a capillary rheometer. DSC studies show that the copolyester has a crystalmesophasic and a broad mesophasic-isotropic transition at 170°C and 220°C. Optical texture observations show the mesophase is characterized by line defect textures, which are characteristic of a nematic structure. At 220°C, both isotropic and nematic phases coexist with the latter being the major. As temperature reaches 250°C, a clear dominance of isotropic phase is observed. At this temperature, the nematic phase of irregular shapes randomly disperses within the isotropic matrix. Subsequent rheological studies were thus conducted in crystal/nematic biphase, single nematic phase, nematic/isotropic biphase, and the near single isotropic phase. Dynamic strain sweep measurements show that a linear viscoelastic region exists at all temperatures tested. The maximum strain amplitude for the linear viscoelastic region is found to be highly structure dependent; it is > 100% in the nematic phase, ∼20% in the biphases, and only about 5% in the isotropic phase. The concurrence of curves obtained at different temperatures in a Cole-Cole plot of G′ vs. G″ indicates similar structures in the nematic phase and biphases. Measurements of steady shear viscosity using a rotational rheometer and a roundhole capillary rheometer show that in the nematic phase the copolyester behaves as a shear thinning fluid for a wide shear rate range of 1 ∼ 10,000 s⁻¹, in which the power law index is about 0.6 ∼ 0.8, and the viscosity is < 10 Pa.s at shear rates >1 s⁻¹.     

Rheological properties of concentrated solutions of agarose in ionic liquid

The rheological properties of agarose solutions were examined under the effect of entanglement coupling between agarose chains. Agarose solutions were prepared by using an ionic liquid 1‐butyl‐3‐methylimidazolium chloride as a solvent. The concentration of agarose was varied from 1.1 × 10¹–2.1 × 10² kg m^?3. The master curves of the angular frequency (ω) dependence of the storage modulus (G′) and the loss modulus (G″) showed a rubbery region in the middle ω region and a flow region at low ω region, respectively. The molecular weight between entanglements (M_e) for agarose was calculated from the plateau modulus. Moreover, M_e for agarose melt was determined to be 2.3 × 10³ from the concentration dependence curve of M_e. By using well‐known empirical relations in polymer rheology, information on molecular characteristics of sample agarose was derived. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheological characterization of the gel point in polymer‐modified asphalts

In this work, the rheological characterization of the gel point in polymer‐modified asphalts is carried out. The viscoelastic properties of polymer‐modified asphalts, in which the polymer is styrene–ethylene butylene–styrene (SEBS) with grafted maleic anhydride (MAH), were measured as a function of MAH concentration. The crosslinking reaction that leads to gelation is characterized by power‐law frequency‐dependent loss and storage modulus (G″ and G′). The relaxation exponent n (a viscoelastic parameter related to the cluster size of the gel) and gel strength S (related to the mobility on the crosslinked chain segments) were determined. The value of the power‐law exponents depends on the composition of polymer, ranging from 0.30 to 0.56, while the value of the rigidity modulus at the gelation point (S) increases with the amount of reactive groups of the modifier polymer. Both n and S are temperature‐dependent in the blends. The blends containing gels present a coarse morphology, which is related to the rheological properties of the matrix and dispersed phase. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Gelation studies on acrylic acid‐based hydrogels via in situ photo‐crosslinking and rheology

The gelation characteristics of acrylic acid (AA)‐based hydrogels were investigated using real time in situ photocrosslinking and rheological measurements. The gel point and gelation times were established using Winter–Chambon criteria. Frequency independence of tan δ was observed in all cases, such that G′ and G″ scaled as ～ωⁿ. The Flory–Stockmayer theory was used alongside other indices in order to probe the gelation and the post‐gelation characteristics of the critical gels and the fully formed hydrogels. Network relaxation exponents (n) were influenced by the concentrations of AA and methylene bis‐acrylamide. The gel stiffness (S) decreased with an increase in the concentration of the monomer and of the concentration of the crosslinker, while network branching decreased (lower fractal dimensions) at the gel point. The conversion at the gel point was found to be iso‐conversion with respect to the intensity of the UV irradiance used in the photocrosslinking reactions (1–20 mW/cm²). Thus, network clusters and the crosslinking reaction mechanism were the same irrespective of radiation intensity, although the rates of the reactions were affected. Having sufficient amounts of reactive species at the time of cure drive the crosslinking reactions beyond the gel point to greater crosslink density and smaller mesh sizes. The effects of auto‐acceleration and free‐volume were observed and shown to have key effects on the gelation mechanisms and the branching topographies of the network, when the concentration of the known polyacrylamide medium were not controlled. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46691.     

Enhanced wear resistance of ultra-high molecular weight polyethylene fibers by modified-graphite oxide

A simple and feasible method to enhance the wear resistance of ultra-high molecular weight polyethylene (UHMWPE) fibers was reported. The graphite oxide (GO) prepared using improved Hummer's method was surface modified with hexadecylamine to improve its compatibility with UHMWPE. Combined with well-dispersion of modified-GO (m-GO) in dichloromethane and the fact that the viscosity of UHMWPE suspension can be decreased by dichloromethane, the well dispersed m-GO/dichloromethane was added into UHMWPE suspension to improve m-GO dispersion in UHMWPE fibers. Finally, UHMWPE fibers with different m-GO concentration were prepared using gel spinning technology. The effect of m-GO concentration on the structure and properties of modified UHMWPE fibers were investigated. The results indicated that the melting temperature and crystallinity of m-GO modified UHMWPE fibers increased with increasing of m-GO concentration, while the fiber's crystal sizes and orientation increased, thus the tensile strength of m-GO modified UHMWPE fibers remained almost undamaged. The introduction of m-GO is beneficial to the formation of smooth transfer film on fiber's surface, which enhanced the self-lubrication of UHMWPE fibers. Compared with pure UHMWPE fiber, the UHMWPE fiber containing 1.5 wt% m-GO had enhanced wear resistance by 55.4% and still maintained high tensile strength of 29.98 cN dtex⁻¹.     

Rheological properties of UHMWPE/HDPE blend gels and morphology and mechanical properties of gel-spun fibers

To produce polyethylene (PE) fibers with relatively high tensile strength but low cost, ultra-high-molecular-weight polyethylene (UHMWPE)/high-density polyethylene (HDPE) (UH) blend gels were prepared from paraffin oil and further fabricated into UH blend fibers by gel spinning. This research focused on the rheological properties of UH blend gels with high solid contents (SCs) ranging from 25 to 100 g/L, as well as morphology and mechanical properties of resultant gel-spun UH blend fibers. The rheological measurements indicated that the apparent viscosity, shear storage, and loss moduli of the UH blend gels were not markedly increased compared with those of the UHMWPE gel with much less SC. No obvious solid–liquid phase separation occurred in UH blend gels at a temperature above the sol–gel transition temperature. UH blend fibers were prepared by drawing as-spun fibers (draw ratio [λ] = 3) at 110°C to λ = 15, 45, 60, and 80, respectively. The orientation degree of fibril structure in UH blend fibers increased with increasing λ but the length of fibrils (L_fibril) showed a complex change. The L_fibril of UH blend fibers became larger due to chain arrangement in company with the transformation of the kebab structure to the extended shish structure when the λ was less than 45 but decreased during further elongation (λ = 60 and 80) because of fibril breakage and recrystallization. The change in morphological behavior led to the corresponding change in mechanical properties of resultant gel-spun UH blend fibers. The tensile strength of gel-spun UH55-45 blend fiber (UHMWPE/HDPE = 5/5 and λ = 45) reached 15.6 cN/dtex, which could fulfill the requirement of mechanical properties in common application.