Online shear viscosity and microstructure of PP/nano-CaCO<Subscript>3</Subscript> composites produced by different mixing types

In this work, the online melt shear viscosity of polypropylene/nano-calcium carbonate composites was measured during the compounding to investigate the relationship between their rheological behavior and microstructure. Effects of dispersive mixing, distributive mixing, and chaotic mixing on online shear viscosity and microstructure of nanocomposites were analyzed. The results showed that the online shear viscosity of nanocomposites is lower than that of pure PP, when the nano-CaCO₃ content is lower than 5, 10, and 15 wt%, compounded by high dispersive mixing, dispersive/distributive mixing, and dispersive/distributive/chaotic mixing, respectively. This is greatly related with the dispersion of nanoparticles in PP matrix. It is deduced that there exists a critical percentage (Φ_cr) of the nano-CaCO₃ with size lower than 100 nm and a critical mean diameter (d _cr). The shear viscosity is lower than that of pure PP when the percentage is higher than the critical percentage and the mean diameter is lower than the critical diameter. In this work, the critical percentage is 80% and critical mean diameter is 60 nm.     

Preparation and characterization of progesterone dispersions using supercritical carbon dioxide

Context: Supercritical fluid methods offer an alternative to conventional mixing methods, particularly for heat sensitive drugs and where an organic solvent is undesirable.

Objective: To design, develop and construct a unit for the particles from a gas-saturated suspension/solution (PGSS) method and form endogenous progesterone (PGN) dispersion systems using SC-CO₂.

Materials and methods: The PGN dispersions were manufactured using three selected excipients: polyethylene glycol (PEG) 400/4000 (50:50), Gelucire 44/14 and D-α-tocopheryl PEG 1000 succinate (TPGS). Semisolid dispersions of PGN prepared by PGSS method were compared to the conventional methods; comelting (CM), cosolvent (CS) and physical mixing (PM). The dispersion systems made were characterized by Raman and Fourier transform infrared (FTIR) spectroscopies, X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), PGN recovery, uniformity and in vitro dissolution, analyzed by high-performance liquid chromatography (HPLC).

Results: Raman spectra revealed no changes in the crystalline structure of PGN treated with SC-CO₂ compared to that of untreated PGN. XRPD and FTIR showed the presence of peaks and bands for PGN confirming that PGN has been incorporated well with each individual excipient. All PGN dispersions prepared by the PGSS method resulted in the improvement of PGN dissolution rates compared to that prepared by the conventional methods and untreated PGN after 60 min (p value?Conclusion: The novel PGN dispersions prepared by the PGSS method offer the great potential to enhance PGN dissolution rate, reduce preparation time and form stable crystalline dispersion systems over those prepared by conventional methods.     

Dispersion and rheology of carbon nanotubes in polymers

We review two generic mechanisms of dispersion of carbon nanotubes in a low-viscosity solvent or high-viscosity polymer, focusing on the neat nanotubes not surface-functionalized in any way. We give estimates of the van der Waals energies involved in nanotube aggregates and examine two main techniques: ultrasonication and shear mixing. For ultrasonic dispersion methods, the local mechanical energy applied to individual tubes is high and bundle separation is assured in the cavitation regime. We analyze and estimate the tube scission during ultrasonic cavitation and predict the characteristic nanotube length L _lim below which scission does not occur. For shear-mixing, our analysis suggests that dispersion is possible in non-parallel bundled nanotube aggregates, in high-viscosity polymers, once a critical mixing time t* is reached. We then examine characteristic features of nanotube-polymer composite rheology and its aging/stability against re-aggregation. We show that at nanotube loading above overlap concentration the tubes form an elastic network in the matrix. Physical junctions of this network are strong and stable enough to provide a rubber-like elastic response with very slow relaxation.     

Shear-thickening behaviour of concentrated polymer dispersions under steady and oscillatory shear

The rheological behaviour of a 58 vol.% dispersion of styrene/acrylate particles in ethylene glycol was investigated using a plate-on-plate rheometer. Experimental results showed that the concentrated polymer dispersion exhibited a strong shear-thickening transition under both steady shear and dynamic oscillatory conditions. The low-frequency dynamic oscillatory behaviour could be reasonably interpreted in terms of the steady shear behaviour. Accordingly, the critical dynamic shear rate [(g)\dot]_{\textc_d} , \dot{\gamma }_{{{\text{c\_d}}}} , agreed well with the critical shear rate obtained in steady flow [(g)\dot]_{\textc_s} , \dot{\gamma }_{{{\text{c\_s}}}} , where [(g)\dot]_{\textc_d} \dot{\gamma }_{{{\text{c\_d}}}} was calculated as the maximum shear rate by the critical dynamic shear strain γ _c and the frequency ω, i.e. [(g)\dot]_{\textc_d} = wg_\textc . \dot{\gamma }_{{{\text{c\_d}}}} = \omega \gamma_{\text{c}} . However, during high-frequency dynamic oscillation, it was observed that the shear thickening occurred only when an apparent critical shear strain was reached, which could not be fully explained by the wall-slipping effect. Based on freeze fracture microscopic observations, the effect of the micro-sized flocculation of particles on the rheology of concentrated dispersions was also discussed.     

The Effect of Shear Mixing Speed and Time on the Mechanical Properties of GNP/Epoxy Composites

The aim of this study was to examine the effect of shear mixing speed and time on the mechanical properties of graphene nanoplatelet (GNP) composites. Shear mixing is cited in the literature as one method of making a good dispersion of nanofillers in a polymer that breaks down agglomerates into smaller particles and in the case of GNP can exfoliate layers of graphene. In this paper 0.1 to 5 wt% GNP was mixed with epoxy at different speeds and for different lengths of time. The composites were then cured and the tensile strength and Young’s modulus was measured. Optical microscopy was performed to examine the dispersion of the GNP in the epoxy. The results show that the shear mixing speed and time affect the size of agglomerates, which has an impact on the mechanical properties of the composite. At 3000 rpm and 2 h of mixing the average size of agglomerate was 26.3 μm (30 % reduction compared to that of 1000 rpm and 1 h duration), the tensile strength of epoxy was not affected by the addition of GNP, while a 12 % increase was recorded for the Young’s modulus. It is also found that functionalisation of the surface of the GNP improves the bond formed between the GNP and the resin that enhances its mechanical properties with no effect on the size of the agglomerates. Acetone was used to improve the GNP dispersion and found that shear mixing 5 wt% of GNP with acetone increases the Young’s modulus up to 3.02 from 2.6 GPa for the neat epoxy, an almost 14 % rise.     

Evaluation and verification of the virgin–recycled mixing ratio of polypropylene plastic

This study has analyzed the properties of blended polypropylene (PP) specimens and employed statistical analysis to develop a method for determining the virgin–recycled mixing ratio of a specimen. Morphological observations and analyses of thermal and mechanical properties were conducted to examine specimen properties. The results were incorporated into regression analysis to create relationship equations. The results revealed that the melt temperature ranged between 167 and 169 °C, melt index (MI) ranged between 7.59 and 18.36 g/10 min, viscosity decreased when the amount of recycled PP and the rotation speed increased, the maximum decomposition temperature decreased with an increase in recycled PP content and increased with the heating rate, activation energy (E_a) ranged between 39.91 and 12.07 kcal/mol, Young’s modulus ranged between 1121.1 and 1910.2 MPa, and impact strength ranged between 37.94and 49.41 J/m (no significant trends). Scanning electron microscopy showed unbroken fibrils distributed on the fracture surface of Specimens 1–3. Additionally, the tensile strain of these specimens was comparatively high. The fracture surfaces of the specimens showed favorable compatibility after undergoing impact tests. The results of regression analysis indicated that the mixing ratio achieved significant correlations with E_a, MI, and Young’s modulus. Thus, regression and multiple regression analysis were performed to create relationship equations.     

Effect of processing variables on thermal and viscoelastic properties in TGDDM/DDS epoxy system

Abstract

The effects of processing temperature and mechanical mixing speed on glass transition temperature, and pot life, activation energies for chemical reaction and molecular relaxation of diaminodiphenyl sulphone (DDS) cured tetraglycidyl diaminodiphenyl methane (TGDDM) epoxy have been evaluated. Viscometry study indicates that the pot life of TGDDM/DDS resin mixtures is significantly affected by the cure temperature and mixing speed. The anomalous behavior at the mixing speed of 900 rpm is likely to be due to a result of poor mixing. Differential scanning calorimetry (DSC) studies show that the glass transition temperature of uncured resin exhibits a T_go of 5 ‐ 19 °C, which decreases with increasing mixing speed. In general, a higher mixing speed would create a higher mixing power of the system, is a result of increasing fluid molecular friction and shear stress. This may be a consequence of molecular chain scissions of oligomer that probably reduce the average molecular weight, and therefore reduce the glass transition temperature. The activation energy for the curing reaction of this epoxy system, around 91 ‐ 98 kJ/mole, was found to be only slightly affected by the mixing speed. Dynamic mechanical analysis (DMA) studies show that two main relaxations can be ob‐ served for this epoxy system. The low temperature relaxation at ‐20 ‐ ‐50 °C is the β transition, with a low activation energy of about 56 ‐ 59 kJ/mole under increasing mixing speed, whereas the high temperature relaxa‐tion at 230 ‐ 260 °C is the a transition, which is associated with the glass transition temperature, with an activation energy of 240 ‐ 400 kJ/mole, and was strongly affected by the mixing speed. It is believed that these activation energies provide a unique method of characterizing the molecular segmental motion of epoxy networks which were affected by the mixing process.     

Investigation on reliability of nanolayer-grained Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> via Weibull statistics

Weibull modulus of bending strength of nanolayer-grained ceramic Ti₃SiC₂ was estimated with over 50 specimens, using the least square method, the moment method and the maximum likelihood technique, respectively. The result demonstrated that the m-value of this layered ceramic ranged from 25 to 29, which is much higher than that of traditional brittle ceramics. The reason of high Weibull modulus was due to high damage tolerance of this material. Under stress, delamination and kinking of grains and shear slipping at interfaces give this material high capacity of local energy dissipation and easy local stress relaxation, leading to the excellent damage tolerance of Ti₃SiC₂. The effect of amounts of specimens on the reliability of the estimated m-values was also investigated. It was confirmed that the stability of the estimated m-value increased with increasing numbers of specimens. The parameter obtained using the maximum likelihood technique showed the highest reliability than other methods. The ranges of failure probability were determined using the Weibull estimates calculated from the maximum likelihood technique.     

Quantitative study of the dispersion degree in carbon nanofiber/polymer and carbon nanotube/polymer nanocomposites

Quantitative measurements of the filler dispersion degree of carbon nanofiber (CNF) and nanotube (CNT) reinforced polymer nanocomposites have been made by transmission electron microscopy. Samples were prepared by either high-shear mixing or twin-screw extrusion processing. It was found that the filler dispersion degree was largely influenced by the filler size. As the filler dimension became smaller, the dispersion parameter D_0.1 largely decreased as quantified, which demonstrated the challenges associated with improving the dispersion of smaller fillers. This work provided a method to quantitatively compare the dispersion degrees of CNF/CNT polymer nanocomposites.     

Physical,mechanical, and biodegradable properties of meranti wood polymer composites

In-situ polymerization and solution casting techniques are two effective methods to manufacture wood polymer composites (WPCs). In this study, wood polymer composites (WPCs) were manufactured from meranti sapwood by solution casting and in-situ polymerization process using methyl methacrylate (MMA) and epoxy matrix respectively. Physical, mechanical, and morphological characterizations of fabricated WPCs were then carried out to analyse their properties. Morphological properties of composites samples were analyzed through scanning electron microscopy (SEM). The result reveals that in-situ wood composite exhibited better properties compared to pure wood, 5% WPC and 20% WPC. Moreover, in-situ WPC had lowest water absorption and least biodegraded. Conversely, pure wood shown moderate mechanical strength, high biodegradation and water absorption rate. In term of biodegradation, earth-medium brought more severe effect than water in deteriorating the properties of the specimens.     

Manufacture of Slow-Release Matrix Granules by Wet Granulation with an Aqueous Dispersion of Quaternary Poly(meth)acrylates in the Fluidized Bed

ABSTRACT

Slow-release matrix granules were manufactured in the fluidized bed using an aqueous dispersion of quaternary poly(meth)acrylates (Eudragit® RS 30 D) as binder for granulation. A factorial design was carried out to investigate the influence of the following parameters, spraying rate, applied polymer amount, and inlet air temperature, on various granule properties. Prerequisites for a slow release of the model drug theophylline are high spraying rate, high amount of polymer, and low inlet air temperature. No considerable decrease of the drug release rate can be achieved without a subsequent curing of the dry granules. A clear correlation exists between the moisture content of the fluidized bed, indicated by the terminal moisture content (TMC), and the mean dissolution time for 80% of the drug (MDT₈₀).     

Synthesis and electrorheological properties of polyaniline/silicon dioxide composites

This study was to synthesize the inherently conductive polymer polyaniline using an optimized process to prepare polyaniline/silicon dioxide (PANI/SiO₂) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/SiO₂ composite films were prepared by drop-by-drop and spin-coating methods. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the SiO₂ were well-dispersed and isolated in composite films. The electrorheological (ER), characteristics of the PANI/SiO₂ composites were investigated. A volume fraction series (φ = 5–25 %) of the PANI/SiO₂/silicone oil dispersions were prepared and sedimentation stabilities were determined. An ER activity was observed from the samples, when subjected to external electric field strength thus, they were classified as smart materials. Some parameters affecting the ER properties of the dispersions such as volume fraction, shear rate, electric field strength, frequency, and temperature were investigated.     

Use of precipitated silica with silanol groups as an inorganic chain extender in polyurethane

In this study, novel polyurethane/silica (PU/SiO₂) hybrid materials, prepared without an external crosslinking agent, were developed via the chemical reaction between urethane groups of PU prepolymer and hydroxyl groups at the surfaces of silica. The added inorganic filler-silica thus played the dual roles not only inorganic chain extender but also reinforcing agent in the preparation of the hybrid. Two different blending methods, were compared with respect to the mechanical properties of the PU/SiO₂ hybrid materials: stirring mixing and three-roller shear mixing. The hybridization mechanism was confirmed using Fourier-transform infrared spectroscopy (FT-IR), solid-state ²⁹Si NMR spectroscopy and X-ray diffraction (XRD). The dispersion of silica particles in the PU matrix was investigated by scanning electron microscopy (SEM). Because of the shear effect of three-roller shear process, the size of the silica aggregates tended to be more uniform. The tensile strength and elongation at break of the PU/SiO₂ hybrid were 51 MPa and 590%, respectively, which represent increases of fourfold and 39% compared to those of neat PU. The thermogravimetric analysis (TGA) results for the PU/SiO₂ hybrids indicated greater thermal stabilities and lower decomposition rates after hybridization. This work contributes new insights into the preparation of high-performance PU/SiO₂ hybrids.     

Electrical conductivities of polypyrrole reacted with dopant solutions

Polypyrrole was prepared by chemical methods (in water by mixing a solution of pyrrole with an oxidizing solution of FeCl₃) and by electrochemical methods. FTIR spectroscopy was used for determining the structure and reaction mechanisms. The main aims were first to prepare some conductive polymers by applying new, efficient, and effective methods to obtain high percent conversions and then to obtain maximum conductivity for each polymer by varying the reactant concentrations. After finding the most effective reactant concentrations, and adjusting molar ratios to improve the conductivity to higher values, the system was treated with different dopants such as ClO₄ ^- ion, I₂, and p-toluene sulfonic acid sodium salt. For each dopant-monomer system, the most effective dopant concentration has been determined. Received: 11 December 2000 / Revised and accepted: 13 December 2000     

Comparison Between Using Longitudinal and Shear Waves in Ultrasonic Stress Measurement to Investigate the Effect of Post-Weld Heat-Treatment on Welding Residual Stresses

Fusion welding is a joining process widely used in the industry. However, undesired residual stresses are produced once the welding process is completed. Post-weld heat-treatment (PWHT) is extensively employed in order to relieve the welding residual stresses. In this study, effect of PWHT time and temperature on the residual stresses of a ferritic stainless steel is investigated. Residual stress distributions in eight welded specimens were measured by using an ultrasonic method. Ultrasonic stress measurement is a nondestructive method based on acoustoelasticity law, which correlates mechanical stresses with velocity of an ultrasonic wave propagating within the subject material. The ultrasonic wave employed could be longitudinal or shear wave produced by the longitudinal (normal) or transverse (shear) transducers, respectively. Ultrasonic stress measurements based on longitudinal waves use longitudinal critically refracted (L_CR) waves in this direction, while shear wave methods use an ultrasonic birefringence phenomenon. The results show that the effect of PWHT can be successfully inferred by both longitudinal and shear wave methods, but the former is found to be more sensitive to stress variation. Furthermore, the distribution of subsurface residual stresses is found to be more distinguishable when the L_CR method is employed.     

Epoxy nanodielectrics fabricated with in situ and ex situ techniques

In this study, we report fabrication and characterisation of a nanocomposite system composed of a commercial resin and extremely small (several nanometres in diameter) titanium dioxide particles. Nanoparticles were synthesised in situ with particle nucleation occurring inside the resin matrix. In this nanodielectric fabrication method, the nanoparticle precursor was mixed to the resin solution, and the nanoparticles were in situ precipitated. Note that no high shear mixing equipment was needed to improve particle dispersion – nanoparticles were distributed in the polymer matrix uniformly since particle nucleation occurs uniformly throughout the matrix. The properties of in situ nanodielectrics are compared to the unfilled resin and an ex situ nanocomposite. We anticipate that the presented in situ nanocomposite would be employed in high-temperature superconductivity applications. In additions, the improvement shown in the dielectric breakdown indicates that conventional high-voltage components and systems can be reduced in size with novel nanodielectrics.     

Interlaminar shear behavior of unidirectional glass fiber (U)/random glass fiber (R)/epoxy hybrid and non-hybrid composite laminates

The interlaminar shear behavior of unidirectional glass fiber (U)/random glass fiber (R)/epoxy hybrid composites was studied with short beam shear bending test. Random glass fiber (R)/epoxy means chopped fiber composite having short discontinuous fiber randomly dispersed in epoxy matrix. The effect of stacking sequence and unidirectional glass fiber relative volume fraction (V_fU/V_fT) on the interlaminar shear strength (ILSS) of the manufactured composites has been investigated experimentally and theoretically. The laminates were fabricated by hand lay-up technique with 5 plies. Two non-hybrid composite laminates [R]₅ and [U]₅ were fabricated using the same fabrication technique for the comparison purpose. The average thickness of the manufactured laminates is 5.5 ± 0.2 mm and the total fiber volume fraction (V_fT) is 37%. Failure modes of all specimens were investigated. Experimental results indicated that the ILSS of [U]₅ is higher than those of hybrid and [R]₅ composite. Hybrid composites have higher ILSS than that of random composites. The stacking sequence and (V_fU/V_fT) ratio have a detectable effect on ILSS of the investigated composites.     

Effect of loading and geometry on the subsonic/intersonic transition of a bimaterial interface crack

An experimental investigation was conducted to study the nature of intersonic crack propagation along a bimaterial interface. A single edge notch/crack oriented along a polymer/metal interface was loaded predominantly in shear by impacting the specimen with a high velocity projectile fired from a gas gun. The stress field information around the propagating crack tip was recorded in real time by two different optical techniques--photoelasticity and coherent gradient sensing, in conjunction with high speed photography. Intersonic cracks on polymer/metal interfaces were found to propagate at speeds between the shear wave speed (c_s) and of the polymer. The nature of the crack tip fields during subsonic/intersonic transition and the conditions governing this transition were examined. Experimental observations showed the formation of a crack face contact zone as the interfacial crack speed exceeds the Rayleigh wave speed of the polymer. Subsequently, the contact zone was observed to expand in size, shrink and eventually collapse onto the intersonic crack tip. The recorded isochromatic fringe patterns showed multiple Mach wave formation associated with such a scenario. It is found that the nature of contact zone formation as well as its size and evolution differ substantially depending on the sign of the opening component of loading.     

The effect of silane coupling agent on the sliding wear behavior of nanometer ZrO<Subscript>2</Subscript>/bismaleimide composites

The polymer composites filled with nanoparticles have good friction and wear properties and widely used in many fields. The performances of nanocomposites are influenced extensively by the nanoparticles morphology, size, volume fraction and dispersion. Nanometer ZrO₂ particles have good properties, lower prices and shows good foreground in resist-materials of polymer composites. In this paper, the nanometer ZrO₂ particles are treated by silane coupling agent of N-(2-aminoethyl)-γ-aminopropylmethyl dimethoxy silane. The effect of nanometer ZrO₂ content and silane coupling agent on the friction and wear properties of BMI copmposites filled with nanometer ZrO₂ are investigated. The composites filled with untreated ZrO₂ and treated ZrO₂ are prepared by the same way of mechanical high shear dispersion process and casting method. The sliding wear performance of the nanocomposites is studied on an M-200 friction and wear tester. The experimental results indicate that the frictional coefficient and the wear rate of the composites can be reduced by filled with nanometer ZrO₂. The composites containing treated nanometer ZrO₂ have the better tribological performance than that containing untreated nanometer ZrO₂. The results are explained from the SEM morphologies of the worn surface of matrix resin and the composites containing nanometer ZrO₂ and the TEM photographs of the nanometer ZrO₂ dispersion in the matrix.     

Investigation of fracture mechanism of 6063 aluminum alloy under different stress states

Fracture mechanisms in a 6063 aluminum alloy were investigated and analyzed carefully by in-situ tensile tests in SEM with a vacuum chamber. Specimens used were designed to produce different stress states. Studies indicated that with stress triaxiality (σ _m/σ _e) decreasing, the fracture modes changed from normal fracture to shear fracture and the fracture surfaces changed from the dimples and intragranular dominated fracture mode to the shear dominated fracture mode. The grain boundaries of the 6063 aluminum alloy were the weakest positions. In the case of high stress triaxiality, the grain boundary cracks were produced by normal stress or by the incompatibility of deformation between neighboring grains, and the normal stress dominated the crack propagation. In the case of low stress triaxiality, the boundary cracks were produced by the relative slipping of grains against neighboring grains, and the shear stress dominated the crack propagation. The final fracture of the specimens occurred by connections of cracks through transgranular cracking of the ligaments among these cracks.