Melt flow behavior of polypropylene composites filled with multi-walled carbon nanotubes during extrusion

Polypropylene (PP) composites filled with multi-walled carbon nanotubes (MWCNTs) were prepared using a twin-screw extruder. The melt flow properties of the composites were measured with a capillary rheometer in a temperature range from 180 to 230 °C and at various apparent shear rates varying from 100 to 4000 s⁻¹. The results showed that the melt shear stress increased almost linearly while the melt shear viscosity decreased almost linearly with increasing shear rates in a bi-logarithmic coordinate system. The melt shear flow followed the power law relationship and the dependence of the melt shear viscosity on temperature obeyed the Arrhenius equation. The relationship between the melt shear viscosity and the MWCNT weight fraction was roughly linear under the investigated range of temperature or shear rate.     

Thermal behavior,dynamic mechanical properties and rheological properties of poly(butylene succinate) composites filled with nanometer calcium carbonate

PBS/nano-CaCO₃ composites with various nano-CaCO₃ weight fractions were prepared by melt blending. The thermal behavior, dynamic mechanical properties and rheological properties of the composites were investigated. DSC measurements revealed that the nano-CaCO₃ particles had little influence on the crystallization and melting behavior of PBS. Thermogravimetric analysis showed that the introduction of nano-CaCO₃ tended to improve the thermal stability of PBS. Dynamic mechanical analysis showed that the G′ and G″ of the PBS/nano-CaCO₃ composites were improved significantly when the nano-CaCO₃ content was not more than 3wt%, while the G′ and G″ were mainly decided by the PBS matrix when the nano-CaCO₃ content exceeded 3wt%. Rheological results showed that G′ < G″ over the frequency range, illustrating the viscous behavior of the samples. The η* of all the samples remained almost constant when the frequency was not more than 0.25 rad/s, which showed the characteristic of a Newtonian fluid. A strong shear thinning effect was observed for all the samples when the frequency exceeded 0.25 rad/s. Furthermore, the microstructure and the relaxation mechanism of the PBS/nano-CaCO₃ composites mainly depended on the PBS matrix.     

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.     

The melt elastic behavior of polypropylene/glass bead composites in capillary flow

The melt extrudate swell and entry pressure losses are important characteristics of elastic properties during die extrusion of polymeric fluids. They are usually expressed with die-swell ratio (B) and entry pressure drop (ΔP_o). In the present paper, the die-swell behavior and entrance pressure drop of a polypropylene (PP) filled with A-glass beads were investigated by using a Rosand capillary rheometer to identify the effects of the filler contents and extrusion rate on the elastic behavior of the sample melts. The experiments were carried out under the conditions with an apparent shear rate range of 50–10⁴ s⁻¹ and a temperature of 190 °C. The results showed that B increased nonlinearly with increasing shear rate at the wall (γ_w), and increased linearly with the increase of shear stress at the wall (τ_w). With the increase of the volume fraction of the fillers B decreased nonlinearly. Similarly, the entry pressure drop increased linearly with the increase of τ_w, whereas the influence of the filler concentration on ΔP_o was insignificant in this case. Furthermore, B increased as a linear function of ΔP_o, and extension stress (σ_e) increased nonlinearly with increasing γ_w.     

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.     

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.     

Synthesis and characterization of poly1-hexene/silica nanocomposites

SiO₂ nano particles, with particle size of 12 nm, were first modified by substituting surface OH groups with O-hexyl moiety. Then, poly1-hexene/modified-SiO₂ composites with various nano-SiO₂ weight fractions were prepared by three different methods: in situ, solution, and melt methods and designated as PH-SiO₂/Insitu, PH-SiO₂/Sol and PH-SiO₂/Melt, respectively. PH-SiO₂/Insitu samples showed highly uniform particle dispersion up to 30 wt. % of silica while in PH-SiO₂/Sol and PH-SiO₂/Melt samples agglomeration of the silica nanoparticles occurred for filler contents ≥5 wt. % (i.e. 5, 10, 20 and 30 wt%). In the synthesized composites, the storage modulus significantly increased as high as 20.7 times when compared with neat poly1-hexene. Maximum decomposition temperature (T_max) and char yield at 600 °C increased with increasing silica level. Rheological results showed that G^ʹ> G^ʺ over the frequency range, illustrating the elastic behavior of the composite samples. In fact, samples showed the characteristic of a non-Newtonian fluid with a strong shear thinning effect in which η* increased with increasing filler weight fraction. From the results, it can be expected that modified silica could replace silica nanoparticles in polyolefin nanocomposite reinforcement.     

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.     

Rheological behavior of biocomposites of silk fibroin fiber and poly(ε‐caprolactone): Effect of fiber network

Rheological behavior was examined for biocomposites of rod‐like silk fibroin (SF) fiber and poly(ε‐caprolactone) (PCL) to investigate an effect(s) of the SF fiber network therein on the mechanical properties. At 160 °C where PCL was a homogeneous melt, linear viscoelastic tests revealed that the SF/PCL composites hardly relax to behave essentially as elastic solids (more precisely, plastic solids before yielding) at low frequencies. The corresponding equilibrium modulus G₀ increased strongly with the SF volume fraction ?_SF (G₀ ～ ?) and was attributable to the elastic bending of the SF fibers incorporated in the network. The Doi‐Kuzuu model for non‐Brownian rods was modified for the SF/PCL composites by incorporating the rod–rod contact at equilibrium. The G₀ calculated from this model was satisfactorily close to the data, in both ?_SF dependence and magnitude, lending support to the assignment of the composite elasticity to the fiber bending. The storage modulus G′ measured under large‐amplitude oscillatory shear (LAOS) was smaller than the linear viscoelastic G′, and this difference between the linear and nonlinear moduli was enhanced for the composites with a larger SF content and at lower frequencies. This nonlinear effect was attributable to a decrease of the effective fiber–fiber contacts sustaining the elasticity under LAOS. Under steady shear, the SF/PCL composites exhibited nonlinear (plastic) flow behavior associated with the stress overshoot, and their apparent viscosity was comparable to/lower than the viscosity of neat PCL matrix. The overshoot became much less significant on application of a second shear immediately after the first shear, while the overshoot was partly recovered after a quiescent rest between the first and second shears. These nonlinear features were attributable to slippage between shear‐oriented fibers and PCL matrix. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1957–1970, 2009     

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 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.     

Effect of unsaturated hydroxyl-fatty acid modified nano-CaCO3 on the morphological and rheological behavior of PP

A modified nano-calcium carbonate (R-CCR) was prepared by coating a layer of unsaturated hydroxylfatty acid on the surface of CCR powders using a solid state method; the latter were commercial nano-CaCO₃ modified with stearic acid. FTIR studies indicate that the modifier is combined on the surface of CaCO₃. PP/EPDM/nano-CaCO₃ ternary composites were prepared by a melt-mixing method. SEM and TEM were utilized to examine the morphology of the composites. The tensile fractured surface of PP/EPDM/R-CCR showed a fibroid morphology and large-scale yield deformation. The impact fractured surface showed that the amount of cavities in the PP/EPDM/R-CCR system was increased, however their size diminished obviously. R-CCR particles were dispersed uniformly in the PP matrix, and their compatibility was distinctly improved as compared to CCR when the amount of R-CCR was 15 h⁻¹. The tensile strength remained nearly constant (reduced from 27.6 MPa to 27.5 MPa), while the impact strength increased from 9.6 kJ/m² to 15.4 kJ/m² as CCR was replaced by R-CCR. Meanwhile, the bending strength and bending modulus also increased correspondingly. Furthermore, the impact strength of PP/EPDM/R-CCR was maintained at a high level (15.4 kJ/m²), which was more than the sum of that of PP/EPDM and PP/R-CCR (6.6 kJ/m² and 6.1 kJ/m² respectively). This indicates that the R-CCR and EPDM have a significant synergistic toughening effect on PP while maintaining the strength and modulus of virgin PP. Both the storage modulus G′ and loss modulus G″ of PP/EPDM and PP/EPDM/R-CCR composites increase with increasing frequency, but the values of G′ and G″ of the tertiary composite are relatively higher than those of the binary system. The loss factor and viscosity decrease with increasing frequency, but there is little difference between tertiary and binary composites. The apparent viscosity η of the tertiary system containing R-CCR is lower than that of the tertiary system containing CCR and virgin PP. The viscosity of the composites sig-nificantly decreases with increasing shear rate. The mea-sured mechanical properties of the composites indicate that replacing CCR with R-CCR for binary composites could simultaneously enhance the toughness and strength of PP. __________ Translated from Acta Polymerica Sinica, 2008, 4 (in Chinese)     

Direct electrochemistry and electrocatalysis of hemoglobin entrapped in composite matrix based on chitosan and CaCO3 nanoparticles

The direct electron transfer between hemoglobin (Hb) and the underlying glassy carbon electrode (GCE) can be readily achieved via a high biocompatible composite system based on biopolymer chitosan (CHT) and inorganic CaCO₃ nanoparticles (nano-CaCO₃). Cyclic voltammetry of Hb-CHT/nano-CaCO₃/GCE showed a pair of stable and quasi-reversible peaks for HbFe(III)/Fe(II) redox couple in pH 7.0 buffer. The electrochemical reaction of Hb immobilized in CHT/nano-CaCO₃ composite matrix exhibited a surface-controlled process accompanied by electron and proton transfer. The electron transfer rate constant was estimated to be 1.8 s⁻¹. This modified electrode showed a high thermal stability up to 60 °C. The apparent Michaelis–Menten constant was calculated to be 7.5 × 10⁻⁴ M, indicating a high catalytic activity of the immobilized Hb toward H₂O₂. The interaction between Hb and this nano-hybrid material was also investigated using FT-IR and UV–vis spectroscopy, indicating that Hb retained its native structure in this hybrid matrix.     

Experimental investigation of first and second laws in a direct absorption solar collector using hybrid Fe3O4/SiO2 nanofluid

In this study, energy and entropy analysis of a residential-type direct absorption solar collector using hybrid Fe₃O₄/SiO₂ nanofluid is evaluated experimentally. The hybrid nanofluid samples are prepared in the different volume ratios of Fe₃O₄/SiO₂ (25:75, 50:50 and 75:25) and different volume fractions (500 ppm, 1000 ppm and 2000 ppm). The appropriate nanofluid samples for using as the working fluid of the collector are chosen based on the results of stability and optical properties of nanofluid. Then, outdoor thermal performance of collector is investigated using the experimental setup based on EN12975-2. Measurement of nanofluid optical properties using the spectrophotometry method shows that the extinction coefficient of 2000 ppm hybrid Fe₃O₄/SiO₂ nanofluid is on average 10 cm^?1 higher than that of the base fluid. Results of energy analysis display that the collector efficiency is increased by mass flow rate and volume fraction of nanofluid asymptotically. The asymptotic value is about 83% for 2000 ppm hybrid Fe₃O₄/SiO₂ nanofluid. The findings indicate that the variation of exergy efficiency of a direct absorption solar collector with the volume fraction and mass flow rate is similar to energy efficiency. The enhancement of exergy efficiency is 66.4% for mass flow rates of 0.0225 kg s^?1 by increasing the volume fraction from 0 to 2000 ppm. It is also observed that dimensionless entropy generation number is decreased by nanofluid volume fraction and by mass flow rate. The lowest entropy generation number is obtained in the mass flow rate of 0.0225 kg s^?1 and the volume fraction of 2000 ppm. The variation of Bejan number by volume fraction shows that the contribution of pressure drop in entropy generation is insignificant.

     

High‐pressure rheology of polystyrene melts plasticized with CO2: Experimental measurement and predictive scaling relationships

A high‐pressure extrusion slit die rheometer was constructed to measure the viscosity of polymer melts plasticized by liquid and supercritical CO₂. A novel gas injection system was devised to accurately meter the follow of CO₂ into the extruder barrel. Measurements of pressure drop, within the die, confirm the presence of a one‐phase mixture and a fully developed flow during viscosity measurements. Experimental measurements of viscosity as a function of shear rate, pressure, temperature, and CO₂ concentration were conducted for three commercial polystyrene melts. The CO₂ was shown to be an effective plasticizer for polystyrene, lowering the viscosity of the polymer melt by as much as 80%, depending of the process conditions and CO₂ concentration. Existing theories for viscoelastic scaling of polymer melts and the prediction of T_g depression by a diluent were used to develop a free volume model for predicting the effects of CO₂ concentration and pressure on polymer melt rheology. The free volume model, dependent only on material parameters of the polymer melt and pure CO₂, was shown to accurately collapse the experimental data onto a single master curve independent of pressure and CO₂ concentration for each of the three polystyrene samples. This model constitutes a simple predictive set of equations to quantify the effects of gas‐induced plasticization on molten polymer systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3168–3180, 2000     

Highly-sensitive electrochemical sensing platforms for food colourants based on the property-tuning of porous carbon

It is very challenging to develop highly-sensitive analytical platforms for toxic synthetic colourants that widely added in food samples. Herein, a series of porous carbon (PC) was prepared using CaCO₃ nanoparticles (nano-CaCO₃) as the hard template and starch as the carbon precursor. Characterizations of scanning electron microscopy and transmission electron microscopy indicated that the morphology and porous structure were controlled by the weight ratio of starch and nano-CaCO₃. The electrochemical behaviours of four kinds of widely-used food colourants, Sunset yellow, Tartrazine, Ponceau 4R and Allura red, were studied. On the surface of PC samples, the oxidation signals of colourants enhanced obviously, and more importantly, the signal enhancement abilities of PC were also dependent on the starch/nano-CaCO₃ weight ratio. The greatly-increased electron transfer ability and accumulation efficiency were the main reason for the enhanced signals of colourants, as confirmed by electrochemical impedance spectroscopy and chronocoulometry. The prepared PC-2 sample by 1:1 starch/nano-CaCO₃ weight ratio was more active for the oxidation of food colourtants, and increased the signals by 89.4-fold, 79.3-fold, 47.3-fold and 50.7-fold for Sunset yellow, Tartrazine, Ponceau 4R and Allura red. As a result, a highly-sensitive electrochemical sensing platform was developed, and the detection limits were 1.4, 3.5, 2.1 and 1.7 μg L⁻¹ for Sunset yellow, Tartrazine, Ponceau 4R and Allura red. The practical application of this new sensing platform was demonstrated using drink samples, and the detected results consisted with the values that obtained by high-performance liquid chromatography.     

Poly(ε-caprolactone) + unsaturated isophtalic polyester blends: Thermal properties and morphology

Miscibility of blends composed by a linear unsaturated polyester (LUP) with poly(ε-caprolactone) (PCL) of different molecular weights (M_w = 50 × 10³, 18 × 10³ and 2 × 10³) has been studied. The blends were subjected to different thermal treatments and have been studied by FT-IR spectroscopy, differential scanning calorimetry (DSC) and scanning electronic microscopy (ESEM). FT-IR results allow proving the miscibility of the blends at temperatures above the melting temperature of neat PCL. DSC measurements confirm the existence of a crystalline phase corresponding to neat PCL. The crystallization of PCL is observed in a wide range of blends composition, being detected in all the blend compositions when the crystallization time increases. Thermograms show clearly the glass transition temperatures of samples that have been rapidly quenched from the melt. However, the change in the heat flow corresponding to the glass transition temperatures is difficult to detect in samples with high PCL crystallization degree. The analysis of the results indicates that the morphology of the amorphous phase is heterogeneous for LUP + PCL blends and changes depending on the thermal treatment. The ESEM measurements, confirm the heterogeneity of the amorphous phase. The decrease of the molecular weight of the PCL favours the miscibility of the blends.     

Prediction of melt rheological properties from GPC molecular weights

The SCLAIR^® solution polymerization platform produces a wide variety of ethylene-α-olefin copolymers and polyethylene homopolymers. Commercial products exhibit density and melt index values ranging from about 0.920 to 0.962 g/cm³ and 0.3–75 g/10 min respectively. Polymer molecular weight distributions can be tailored to meet a broad selection of end-use requirements. In this study, we have used a chemometric analysis approach using The Unscrambler^® software to demonstrate statistical correlations between rheological properties and fundamental structural parameters for thirty-three commercial SCLAIR polyethylenes. We demonstrate that molten rheological properties such as melt index, stress exponent, zero-shear viscosity, characteristic relaxation time, cross-over modulus and frequency show good non-linear correlations with molecular weight characteristics of SCLAIR products as determined by gel permeation chromatography (GPC). We also show that, with the use of Partial Least Squares (PLS) regression techniques, most melt rheological properties can be accurately predicted on the basis of GPC data.     

Effect of molecular structure on polyethylene melt rheology. II. Shear-dependent viscosity

The investigation of the effect of molecular structural variables on the melt viscosity of polyethylene was extended to the shear dependent region by application of a reduced variables treatment following, in a formal sense, that of Bueche. Viscosity–shear rate data were obtained for a series of experimentally polymerized linear polyethylene samples having a range of molecular weights and molecular weight distributions as characterized primarily by gel permeation chromatography. These data could be superimposed on a single reduced variables flow curve using parameters which were a function only of temperature, limiting Newtonian viscosity, M?_w, and M?_w/M?_n. The same treatment was successfully applied also to branched (low-density) fraction data discussed in a previous paper, with additional correction for long-chain branching. However, different reduced variables curves were obtained for the branched and linear cases.     

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.