Melt flow behavior in capillary extrusion of nanometer calcium carbonate filled PCL bio-composites

Nanosized calcium carbonate (nano-CaCO₃) filled polycaprolactone (PCL) bio-composites were prepared by using a twin-screw extruder. The melt flow behavior of the composites, including the entry pressure drop, melt shear flow curves and melt shear viscosity, were measured through a capillary rheometer operated in a temperature range of 170∼200 °C and shear rates varying from 50 to 10³ s⁻¹. The entry pressure drop showed a non-linear increase with increasing shear stress when the filler weight fraction was less than 3%, while it decreased slightly with an increase of shear stress at a filler weight fraction of 4%. The melt shear flow roughly followed a power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Moreover, the influence of the nano-CaCO₃ on the melt shear viscosity of the PCL composite was not significant at low filler levels.     

Melt extrudate swell behavior of graphene nano-platelets filled-polypropylene composites

The extrudate swell ratios of polypropylene (PP) composite melts filled with graphene nano-platelets (GNPs) were measured using a capillary rheometer within a temperature range of 180–230 °C and apparent shear rate varying from 100 to 4000 s⁻¹ in order to identify the effects of the filler content and test conditions on the melt die-swell behavior. It was found that the values of the extrudate swell ratio of the composites increased with increasing apparent shear rate, with the correlation between them obeying a power law relationship, while the values of the extrudate swell ratio decreased almost linearly with rise in temperature. The values of the melt extrudate swell ratio increased approximately linearly with increasing shear stress, and decreased roughly linearly with an increase of the GNP weight fraction. In addition, the extrudate swell mechanisms are discussed from the observation of the fracture surface of the extrudate using scanning electronic microscopy. This study provides a basis for further development of graphene reinforced polymer composites with desirable mechanical performance and good damage resistance.     

Studies on melt flow properties during capillary extrusion of PP/Al(OH)3/Mg(OH)2 flame retardant composites

The apparent melt shear viscosity of polypropylene (PP) composites filled with aluminium hydroxide (Al(OH)₃) and magnesium hydroxide (Mg(OH)₂) was measured by means of a melt flow rate instrument under experimental conditions of temperature ranging from 170 to 195 °C and load varying from 2.16 to 12.5 kg, to identify the effects of particle size and content. The results showed that the melt shear flow of the composites obeyed the power law under the experimental conditions, the dependence of the melt apparent shear viscosity (η_a) on temperature was consistent with the Arrhenius equation, and the sensitivity of the η_a for the composite melts to temperature increased with addition of flame retardant. The η_a of the composites decreased with increasing apparent shear rate. The η_a increased with an increase of the content of flame retardant, but this rate of increase decreased with a rise of temperature or load. When the particle size of flame retardant was smaller than 5 μm, the η_a of the composites increased with increase of particle size of flame retardant, and then reduced with a further increase of particle size of flame retardant.     

Rheological properties of wood polymer composites at high shear rates

This paper presents the rheological properties of wood-polymer composites (WPC) with a polypropylene (PP) matrix in the corrected shear rate range from approx. 20 s⁻¹ to 150 000 s⁻¹. Tests were conducted using a capillary rheometer and a rheological head of the author's construction, for which the working element is a thermoplastic injection moulding machine. The constructed tool was found to be very useful, especially for the determination of the processing characteristics of WPC composites containing a large particle-size filler. It was observed that the rheological properties of wood-polymer composites in the shear rate range of up to several thousand s⁻¹ significantly depended on the filler content of the polymer matrix; at the same time, at higher shear rate, a clear decrease in the effect of the wood filler content on the viscosity of the composites and on the flow behaviour, as described by the power law, took place.     

Experimental study on viscosity properties of cyclic olefin copolymer (COC) flowing through micro capillary dies

As an emerging polymer, COC has been commonly used to make microfluidic chips by microinjection molding; and in this process, COC melt flows in a trans-scale cavity in which macro and micro scales coexist. Thus, in such a circumstance, understanding viscosity property of COC melt would be helpful to mold design, parameter determination of injection molding and prediction of molding quality. In this paper, viscosity properties of COC melt flowing in three dies with different diameters (500 μm, 200 μm, 100 μm) were investigated at three different temperatures (240 °C, 260 °C, 280 °C) by a capillary rheometer. The results showed that viscosity of COC melt flowing in different micro dies can be reduced significantly by increasing temperature, and visco-temperature property of COC melt could be described by Vogel equation in a considerable accuracy. It was found that temperature sensitivity of viscosity of COC melt varies with shear rate. Besides, as die diameter decreased, viscosity of COC melt was also reduced greatly. Moreover, in 500 μm die, viscosity of COC decreased constantly with shear rate; however, in 200 μm and 100 μm dies, viscosity witnessed an increase within a certain shear rate range. It implies that behavior of COC molecular chains might varies in different micro-scales.     

Rheology of linear and branched styrene–acrylonitrile copolymers. Similarities and differences

A comprehensive investigation of rheological properties of linear and branched styrene-acrylonitrile copolymer specimens with similar molecular characteristics has been carried out. During the steady-state shear flow, the viscosity properties of both specimens are described by the Cross equation. In this case, the branched copolymer is characterized by a higher viscosity and shear thinning degree as well as by substantially lower shear rate values corresponding to transition to the non-Newtonian flow region. The elasticity of the branched copolymer melt (estimated from the value of the first normal stress difference) is considerably higher than that of the linear. This is reflected on the characteristics of occurrence of unstable flow at high shear rates. Rougher extrudate surface distortions are characteristic for the branched copolymer, and the shear rate corresponding to their occurrence is noticeably lower than for the linear copolymer. The dynamic characteristics of the copolymers being compared also attest to a greater elasticity of the branched specimen. An investigation of the viscoelastic properties in a wide temperature range allowed constructing a generalized frequency dependence of dynamic moduli encompassing various regions of the relaxation states of the copolymer specimens. Continuous relaxation spectra were calculated by means of the Mellin transform. It is shown that relaxation phenomena caused by segmental mobility doesn’t depend on the presence of branchings, whereas branching of the chain has a substantial effect on translation mobility of the chain as a whole. Branching leads to a noticeable increase of transient elongation viscosity but has almost no effect of strain hardening of the melt.     

Geometry dependence of the elongation behavior of a polypropylene melt through a micro die

A series of rheological experiments was performed for a polypropylene (PP) melt to explore its elongation behavior through a capillary die. Using an advanced twin-bore capillary rheometer with dies measuring 1.0, 0.5, and 0.25 mm in diameter, the experiments were performed at 210, 220, and 230 °C. The results indicated that the temperature of the PP melt had a significant effect on its extensional viscosity. The different decreases in the extensional viscosity values in the tested dies revealed the geometry dependence of the extensional viscosity. In the case of PP in the 0.25 mm die at 210 °C, the extensional viscosity values under different extensional strain rates were much higher than those in the other dies. Only in the 1.0 mm die did the relationship between the extensional viscosity of PP and its temperature obey the Arrhenius equation due to the larger die size which related to a slight size effect on its elongation behavior. The calculated deviations of the extensional viscosity in the tested dies demonstrated that the increasing pressure applied to the PP melt in the micro channel was related to the geometry dependence of the elongation behavior of the PP melt. The change in the extensional viscosity eventually relied on the interaction of the die geometry, the temperature, and the extensional stress of the PP melt.     

Effect of working temperature on the interfacial behavior of overmolded hybrid fiber reinforced polypropylene composites

In the present study, the interfacial behavior of overmolded hybrid fiber reinforced polypropylene composites (hybrid composites) in the working temperature range from 23 °C to 90 °C was studied by experimental and constitutive methods. Monotonic and cycle loading-unloading single-lap-shear tests were employed to determine the interfacial properties of hybrid composites. The experimental results show that both interfacial shear strength and shear stiffness decrease with increasing working temperature. A regression function was adopted to evaluate the decaying degree of interfacial properties with increasing working temperature. The shear stress-displacement relationship under monotonic loading exhibits nonlinear behavior after an initial elastic region. The envelope lines of shear stress-displacement of hybrid composites under cyclic loading indicate that the nonlinearity in the curve is caused by the plastic deformation of polypropylene in the interphase region. A constitutive model was built to describe the nonlinear shear stress-displacement relation of hybrid composites at different working temperatures. A full suite of temperature-dependent plastic parameters in the model was obtained from cyclic loading-unloading tensile tests. The predicted shear stress–displacement curves agreed well with experimental results from different working temperatures. In addition, the failure mode of hybrid composites varied with working temperature.     

Experimental study on the rheological behavior of nanolubricant-containing MCM-41 nanoparticles with viscosity measurement

In this study, the rheological behavior and viscosity of a stable nanofluid, which is prepared with the suspension of MCM-41 nanoparticles in SAE40 engine oil as base fluid, would be presented. Two-step method has been used to stabilize the nanoparticles in engine oil. To obtain structural and morphological properties of the synthesized nanoparticles, small-angle X-ray scattering, N₂ adsorption/desorption analysis and scanning electron microscopy have been done. Then, viscosity of nanofluids has been measured in temperature range of 25–55 °C, shear rates up to 13,000 s^?1 and different concentrations (0 mass%, 0.5 mass%, 1 mass%, 3 mass% and 5 mass% of MCM-41 nanoparticles). For all the samples, the shear stress versus shear rate diagrams showed that SAE40 oil has Newtonian behavior, in which adding mesoporous silica nanoparticles causes non-Newtonian or pseudoplastic behavior. The results declared that viscosity decreases with increasing temperature and increases with an enhancement in concentration. Furthermore, based on experimental results, an accurate correlation has been proposed to predict the viscosity of SAE40/MCM-41 nanolubricants.

     

Rheological,morphological, thermal,and mechanical properties of blends of vectra A950 and poly(trimethylene terephthalate): A study on a high-viscosity-ratio system

Poly(trimethylene terephthalate) (PTT) and a liquid crystalline polymer, Vectra A950 (VA), were melt-blended and subjected to capillary rheometry. Effects of VA content, shear rate and temperature on viscosity and flow activation energy (E_a) were investigated. Partial fibrillation was found even though the viscosity ratio was greater than one, leading to the formation of in-situ composites. Thermal and thermogravimetric analysis of the blends suggested that they were immiscible and their thermal stabilities were enhanced. From tensile tests, the incorporation of VA improved tensile modulus, slightly decreased tensile strength, and drastically lowered elongation at break, compared to neat PTT. It was found that the blend with the best VA dispersion can be achieved at the minimum VA content (10 wt%) and lowest processing temperature (250 °C). Not only did this blend exhibit improved mechanical properties comparable to those of blends processed at temperatures closer to the crystalline-to-nematic transition of VA (～280 °C), it also shows enhanced processibility through the reduction of both melt viscosity and E_a.     

Rheology of the Melt of Acrylonitrile–Styrene Copolymer Modified with Montmorillonite

The rheological properties of the acrylonitrile–styrene copolymer modified with hydrophobized montmorillonite Cloisite 30B and composites are studied in a wide range of shear rates and shear frequencies at a temperature of 230°C. It is shown that the filler insignificantly affects the viscoelastic properties of the compositions, but the viscosity of composite melts considerably increases at low shear rates and monotonically grows with increasing concentration, whereas at high shear rates the effective viscosity declines appreciably in the concentration range of about 0.3 vol %.     

What is the flow activation volume of entangled polymer melts?

We evaluate the flow activation volume in polymer melts of isotactic polypropylene and atactic polystyrene with step-shear experiments at different melt temperatures. The melt is initially sheared with constant shear rate until the attainment of a melt state with nearly constant viscosity. Perturbations to this experiment, involving shear steps in short-time intervals with decreasing rates, are induced next. Measurements of the shear stress value at each shear rate step allow the evaluation of an experimental (apparent) flow activation volume. The true flow activation volume is evaluated by extrapolating the experimental data to infinite shear stress values. The value obtained is larger than the physical volume of the chain and agrees with the volume of a tube confining chains with a molecular weight between M _n and M _w. Besides supporting the validity of tube model, experiments based on this protocol may be used on model polymer samples, in composites with nanoparticles and in polymer blends to access the validity of mechanisms considered by flow models.     

Rheological properties of styrene–butadiene rubber filled with electron beam modified surface treated dual phase fillers

The rheological properties of styrene–butadiene rubber (SBR) loaded with dual phase filler were measured using Monsanto Processability Tester (MPT) at three different temperatures (100°C, 110°C and 130°C) and four different shear rates (61.3, 306.3, 613, and 1004.5 s⁻¹). The effect of electron beam modification of dual phase filler in absence and presence of trimethylol propane triacrylate (TMPTA) or triethoxysilylpropyltetrasulphide (Si-69) on melt flow properties of SBR was also studied. The viscosity of all the systems decreases with shear rate indicating their pseudoplastic or shear thinning nature. The higher shear viscosity for the SBR loaded with the electron beam modified filler is explained in terms of variation in structure of the filler upon electron beam irradiation. Die swell of the modified filler loaded SBR is slightly higher than that of the unmodified filler loaded rubber, which is explained by calculating normal stress difference for the systems. Activation energy of the modified filler loaded SBR systems is also slightly higher than that of the control filler loaded SBR system.     

熔体黏度对黏土在聚丙烯/聚苯乙烯共混物中优先插层行为的影响

通过熔融共混法在160℃加工条件下制备了聚丙烯/聚苯乙烯/黏土(PP/PS/clay)复合材料.X射线衍射分析(XRD)和透射电镜分析(TEM)的结果表明,黏土在共混物中存在着优先插层现象.黏土优先被PS分子链所插层,且不受PS组分含量和加料方式的影响.基于复合材料中PP和PS组分的熔体黏度对温度敏感性的差别,通过改变加工温度的方法,研究组分的黏度差别对黏土优先插层行为的影响.随共混加工温度的升高,黏土在共混物中的分布位置逐渐从PS相向PP相迁移.TEM和动态黏弹行为测试(ARES)的结果表明,组分间黏度的差别能控制黏土的优先插层行为.组分黏度越高,加工过程中所能传递的剪切应力就越大,插层能力也就越强.     

Melt elongation flow behaviour of LDPE/LLDPE blends

The extensional rheological properties of low density polyethylene (LDPE)/linear low density polyethylene (LLDPE) blend melts were measured using a melt spinning technique under temperatures ranging from 160 to 200 °C and die extrusion velocities varying from 9 to 36 mm/s. The results showed that the melt elongation stress decreased with a rise of temperature while it increased with increasing extensional strain rate and the LDPE weight fraction. The dependence of the melt elongation viscosity on temperature roughly obeyed the Arrhenius equation, it increased with increasing extensional strain rate and the LDPE weight fraction when the extensional strain rate was lower than 0.5 s⁻¹, and it reached a maximum when the extensional strain rate was about 0.5 s⁻¹, which can be attributed to the stress hardening effect.     

Characterization of dental composites by thermal analysis, infrared spectroscopy and scanning electron microscopy

Commercial light-cured dental composites were used in this study. Two laboratorial composites, Resilab (Wilcos/Brazil), Epricord (Kuraray/Japan) were compared under cured and uncured conditions. Thermal analysis, infrared spectroscopy and scanning electron microscopy were used to evaluate the dental composites. The mass change and heat flow signals (TG–DSC) were recorded simultaneously by using STA 409 PC Luxx (NETZSCH), in the 25–800 °C temperature range at a heating rate of 10 °C/min under nitrogen atmosphere (70 mL/min). Employing thermo-microbalance TG 209 C F1 Iris (NETZSCH) coupled to the BRUKER Optics FTIR TENSOR, the samples were analyzed by combined thermogravimetric and spectroscopic methods (TG–FTIR). The initial sample mass was about ~12 mg, the data collection have been done in the 35–800 °C temperature range at a heating rate of 20 K/min in nitrogen atmosphere (flow rate: 40 mL/min). Finally, superficial topographic was analyzed by scanning electron microscopy (SEM). Dental composite evaluation suggests a high thermal stability and inorganic content in RES D sample. Degrees of conversion (DC) values were almost the same and there was no direct relationship between DC and amount of particles and size. Similar compositions were found in all samples.     

Shear-induced non-isothermal crystallization of poly(butylene adipate-co-terephthalate)

The influence of shear on non-isothermal crystallization of commercial poly(butylene adipate-co-terephthalate) (PBAT) was investigated. PBAT melt was sheared at 130 and 150 °C at rates of 10–100/s, and then cooled. The crystallization was followed by a light depolarization technique, whereas the crystallized specimens were analyzed by DSC, 2D-SAXS, 2D-WAXS, PLM and SALS. Shear flow shifted crystallization to higher temperature, and the effect was augmented by lower temperature of shearing as well as by higher shear rate and strain. Crystallization peak rate temperature of PBAT, sheared at 130 °C for 5 min at 100/s, increased by up to 12 °C. However, no evidence of crystal orientation due to shear was found, indicating that the shear induced the point-like nucleation. Only a small increase of melting peak temperatures, by up to 2–5 °C, was observed for the specimens sheared at the highest rates (≥50/s).     

Dynamic and steady-shear melt rheology of and ethylene-methacrylic acid copolymer and its salts

Studies have been made on the dynamic and steady-shear melt rheology of an ethylene–methacrylic acid copolymer and two of its salts obtained by partial neutralization with sodium and with calcium bases. Measurements were made with a Weissenberg rheogoniometer over a broad range of shear rates and frequency in the temperature interval mainly from 100 to 160°C. The temperature coefficients of dynamic and steady shear viscosity are evaluated at both constant shear rate and constant stress. Likewise, complex dynamic viscosities and apparent high steady-flow viscosities and intercompared at equivalent frequencies and shear rates. The un-ionized acid copolymer shows good correlation between the frequency dependence of the complex viscosity and the shear rate dependence of the apparent viscosity. This is not true for either the sodium salt or the calcium salt. These results are consistent with the two-phase structural model for these materials, i.e., a matrix of hydrocarbon in which are embedded ionic domains.     

Viscosity Behaviors of Rapidly Curable Silica Sols

The viscosity behaviors of rapidly curable transparent silica aerogels, such as time at the onset point and the slope of viscosity increase, are investigated as functions of target density, water and catalyst content. Results were compared with the visually measured gel time. The effects of temperature and shear rate on the onset point and rate of the viscosity increase are also investigated with the selected samples. Experimental design and result analysis were also conducted using the Design of Experiment (DOE) method, and the Arrhenius relation was applied to predict the temperature dependence of viscosity. It is found that the target density and catalyst content played more important roles in determining gelation and viscosity behavior than water content did. As the target density increased, the gel time and the onset point appeared at significantly earlier times and the slope increased more rapidly, while there existed an optimum catalyst and water content for fast gelation and desirable viscosity behaviors. The temperature dependence of the viscosity behaviors of rapidly curable transparent silica sols can be expressed by the Arrhenius relation. The onset time of viscosity increase was little affected by the shear rate at a low shear rate range of up to 1.32 s⁻¹, and after that it linearly decreased with increasing shear rate, while the slope of viscosity increase continuously decreased with increasing shear rate. Overall, the viscosity measurement appears as a simple and reliable method for quantitatively measuring gel time, especially for the rapidly curable sol–gel process.     

RHEOLOGICAL PROPERTIES OF LIQUID CRYSTALLINE COPOLY (ρ-HYDR0XYBENZ0ATE/BISPHENOL A TEREPHTHALATE)

Various aspects of the rheological behaviour of liquid crystalline copolyesters, i.e.,samples of copoly (p-hydroxybenzoate / bisphenol A terephthalate), were explored by usingInstron capillary rheometer. The experimental results indicated that the apparent viscositywas affected significantly by shear rate, melt temperature and p-hydroxybenzoate unit con-tent. The flow activation energies △E_η are in the range of 205.1 to 74.5 kJ/mol, dependingon the shear rate of 10-1000 s~(-1), at temperature 568-603K. These copolyesters exhibit ayield phenomenon in the shear flow, and the values of yield stress decrease with increasingtemperature. It is quite unusual that the extrudate of the copolyester shows the smallerswelling ratio even than unity at the lower temperature and lower shear rates.