Phase separation in non-solvent/dimethylformamide/polyethersulphone and non-solvent/dimethylformamide/polysulphone systems

The cloud point curves for the ternary solutions non-solvent/dimethyl-formamide/polyethersulphone and non-solvent/dimethylformamide/polysul-phone were determined by a titration technique, at 303 K. In both systems the following order of increasing non-solvent content at the cloud point was obtained: water < methanol < ethanol < 1-propanol < acetone < carbon tetrachloride. For each non-solvent the cloud point curve for the PES system occurred at higher non-solvent concentrations than for the corresponding PSN system.     

Exploring the effects of non-solvent concentration, jet-stretching and hot-drawing on microstructure formation of poly(acrylonitrile) fibers during wet-spinning

The simultaneous effects of non-solvent concentration in the spinning dope, jet-stretching and hot-drawing on porosity, morphology development and mechanical properties of wet-spun poly(acrylonitrile) fibers were studied. Addition of non-solvent to the spinning dope increased dope viscosity, the entanglement density of the polymeric solution and the number of entanglements per chain. Drawability of the as-spun fiber depended on the number of entanglements per polymer chain. Therefore, addition of non-solvent improved or spoiled drawability of the wet-spun fibers based on the concentration of the initial spinning dope. Hot-drawing and jet-stretching did not affect the fraction of nanovoids but shifted their size distribution towards smaller values. However, hot-drawing was more effective in reducing the overall porosity of the fibers in comparison with jet-stretching. Fiber tenacity increased when overall porosity decreased. Finally, strength-diameter correlation showed good agreement with the Griffith’s theory.     

Fluidized bed chemical vapor deposition of pyrolytic carbon-III. Relationship between microstructure and mechanical properties

Pyrolytic carbon (PyC) coatings with different densities were produced by fluidized bed chemical vapor deposition under different deposition conditions. Their Young’s modulus and hardness were measured by nano-indentation, whereas the deformation behavior was studied through analyzing the force–displacement curves of the indentations. The deformation mechanism of PyC under indentation is attributed to the slip of the graphene planes, and its reversibility is discussed in terms of the defects of the microstructure. We observed a linear relationship between the density of PyC’s and their Young’s modulus and hardness, for densities lower than 1.9 g/cm³. Above this value, the mechanical properties were controlled by the amount of interstitial defects. Samples were also heat treated at 1800 °C and 2000 °C, and their changes in microstructure, hardness and Young’s modulus are discussed as a function of density.     

Process intensification approach for preparation of curcumin nanoparticles via solvent–nonsolvent nanoprecipitation using spinning disc reactor

Continuous preparation of curcumin nanoparticles via solvent–nonsolvent (S-NS) precipitation by using spinning disc reactor was investigated. The process intensification by spinning disc reactor (SDR) along with the comparative study of conventional mechanical agitated contactor was carried out. Solvent used for curcumin precipitation in this study was ethanol whereas non-solvent deionised water. Influences of various operating parameters for spinning disc process; such as flow rate of S-NS, S-NS ratio, concentration of curcumin, disc characteristics, concentration of protecting agent and rotating disc speed were examined on the nanoparticles size. The average optimum curcumin particles size was obtained in the range 180–220 nm in consideration with particles size distribution at a flow rate of 200 mL min⁻¹; curcumin concentration of 0.5 g L⁻¹ in ethanol; polyvinylpyrilodine (PVP) concentration of 1 g L⁻¹ in deionised water; S:NS ratio 1:4 and operating disc speed of 1500 rpm. Particles were characterized by using XRD, FT-IR, DSC and SEM which showed decrease in the crystallinity after the nanoprecipitation of curcumin. The dissolution rates of the fabricated curcumin nanoparticle were found drastically higher than original curcumin.     

Experimental study of particle rotation characteristics with high-speed digital imaging system

Particle rotation plays an important role on several aspects in gas-solid two-phase flow. However, it has not been paid much attention due to a lack of appropriate measurement methods. An attempt has been made in the present paper on the experimental study of particle rotation characteristics in a cold pilot-scale Circulating Fluidized Bed (CFB) riser, by using a high-speed digital imaging measurement system. It is found that one can measure rotation speeds manually for particles with special speckles on their surfaces or irregular shapes by observing particle image sequences. A dual-frequency imaging method was presented to enlarge the maximal measurable rotation speed at finite frame frequency and the measured rotation speeds are validated theoretically. Furthermore, particle rotation characteristics in a cross-section in upper dilute-phase zone were analyzed statistically. The results show that the average particle rotation speed is about 300 rev/s with the top speed of 2000 rev/s, when the superficial gas velocity U_g, external solids mass flux G_s and average particle diameter are 5 m/s, 1.5 kg/(m² s) and 0.5 mm, separately. The average particle rotation speed near the wall area is higher than that in the center area at the testing cross-section. Those particles, with either smaller size or higher radial component of translational speed, may have higher average rotation speed. The average rotation speed of irregular particles is apparently higher than that of the spherical ones.     

Stabilizing of magnesium powder by microencapsulation with azidodeoxy cellulose nitrate

Surface of magnesium particles is highly reactive and may be oxidized easily during storage at ambient conditions. Coating the surface of metal particles with a layer of polymer could be a simple and efficient way to prevent oxidation. In this study, Taguchi robust design was employed as a statistical experiment design for coating of magnesium powder with azidodeoxy cellulose nitrate via solvent/non-solvent technique. FT-IR spectroscopy and scanning electron microscopy techniques were used to evaluate the surface morphology of coated particles. The effect of azidodeoxy cellulose nitrate coating on magnesium powder thermal stability has been investigated by means of thermogravimetry (TG) coupled with differential scanning calorimetry (DSC). The effects of procedure parameters, i.e., type of solvent, percent of polymer as the stabilizer, flow rate of non-solvent addition, and added non-solvent volume in the coating quality and thermal properties of magnesium powder have been studied by thermal analysis methods. Analysis of variance (ANOVA) was employed to evaluate quantitatively the effect of these parameters on thermal stability of coated magnesium particles. Thermal data showed that magnesium powder could be stabilized considerably by controlling coating process parameters including the percent of the stabilizer, flow rate of non-solvent addition, and type of solvent. Based on the ANOVA results, using of 3% stabilizer, 1 ml/min as non-solvent flow rate, and DMF as the solvent are optimum conditions for coating of magnesium particles with azidodeoxy cellulose nitrate leads to producing coated particles with higher thermal stability (567 °C); whereas, TG/DSC analysis results revealed that the main thermal oxidation of the pure magnesium powder starts at lower temperature ranges of 260 °C.     

Influences of polypropylene grafted to SiO<Subscript>2</Subscript> nanoparticles on the crystallization behavior and mechanical properties of polypropylene/SiO<Subscript>2</Subscript> nanocomposites

Influences of polypropylene (PP) grafted to SiO₂ nanoparticles (7 nm) were studied on the crystallization behavior and the mechanical properties of PP/SiO₂ nanocomposites. PP for the matrix and grafting was synthesized in order to have an identical primary structure, aiming at their co-crystallization and resulting reinforcement of filler-matrix interfaces. The grafted PP chains improved the dispersion of SiO₂, and notably accelerated nucleation in crystallization. It was plausible that the grafted chains whose one chain end was pinned to SiO₂ became nuclei of the crystallization (co-crystallization between the matrix and grafted chains), thus directly bridging between the matrix and SiO₂ nanoparticles. The Young’s modulus and tensile strength were most improved by the grafted PP chains at low filler contents such as 2.3 wt%, whose origin was attributed to effective load transfer to SiO₂ through the co-crystallization-mediated bridging.     

Chemically Modified Polyvinyl Butyral Polymer Membrane as a Gel Electrolyte for Lithium Ion Battery Applications

A novel porous membrane of chemically modified polyvinyl butyral (mPVB), with improved thermal properties and chemical stability for lithium ion battery applications, is successfully synthesized by utilizing the chain extension reaction of the OH units from PVB. The porous mPVB membranes are obtained via the tape casting and phase inversion method. The corresponding gel polymer electrolyte (GPE) is achieved by immersing the as‐prepared membranes in the liquid electrolyte. The electrochemical performances of the GPE show that the mPVB membranes have the features of good uniformity, high porosity ( ≈ 90%), great thermal stability, and high mechanical strength. Moreover, the GPE exhibits good chemical stability, a wide electrochemical window, as well as high ionic conductivity ( ≈ 1.21 × 10^?3 S cm^?1). A test of a Li/GPE/LiFePO₄ battery cell shows a capacity of 147.7 mAh g^?1 and excellent cycling stability, demonstrating the great potential of the mPVB‐based GPE for lithium ion battery applications.     

Preparation of an acrylics‐grafted polyester and its aqueous dispersion—Structural study of acrylics‐grafted polyesters

Structural study of two grafted polyesters, which were different in mechanical properties, was investigated by DMA, TEM, and high‐resolution solid‐state ¹³C‐NMR. Using DMA and TEM, a separated phase larger than 100 nm was not found in the grafted polyesters. The main chain and the side chain seemed miscible. Analysis of T_1ρHs and their distributions made the difference of microstructure in the grafted polyesters clear. P(EA‐AA)‐grafted polyester, which was very brittle, had a separated phase in the grafted polyester. The separated phase was estimated to be at a size of about 3 nm. On the other hand, P(St‐DEF‐MAnh)‐grafted polyester, which was very ductile, had a homogeneous microstructure. The difference in the microstructures of the grafted polyesters seemed to effect the mechanical properties of the grafted polyesters. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 392–402, 2000     

Mechanical evaluation of cordierite precursor green bodies obtained by starch thermogelling

The mechanical behavior of green bodies (porous cordierite precursors) obtained from suspensions of kaolin, talc and alumina powders consolidated by starch thermogelling was studied. Different starches were employed as consolidator/binders: potato, cassava, corn or modified cassava.Aqueous suspensions of the powders (29.6 vol.%) with 11.7 vol.% of starches were prepared by intensive mechanical mixing, homogenization and vacuum degasification. Disks were prepared by thermogelling the suspensions for 4 h at 75–85 °C and additional drying. Green bodies were characterized by bulk density and apparent porosity measurements and microstructural analysis by SEM/EDAX.The mechanical evaluation was carried out by diametral compression in displacement control. Apparent stress–strain relations were obtained from load–displacement curves and several mechanical parameters were determined: mechanical strength, apparent Young modulus and yield stress. Crack patterns were analyzed together with fractographic analysis by SEM. Mechanical results were related to the behavior of the starches in aqueous suspension and the properties of the formed gels.     

“SPURT FRACTURE” IN CAPILLARY FLOW

The critical conditions under which flow curves in capillary flow abruptly change their slope to zero (spurt) and the influence of solvent additive and solvent power on this phenomenon have been investigated. Based on a forced high elastic state concept an expression for the so-called spurt phenomenon, i.e. fracture-induced slip at the wall in a capillary of a capillary rheometer, is deduced. It is found that the spurt fracture stress, τ^s _cr, and the spurt fracture shear rate, γ^s _cr, can be represented by the master curve log (τ ^s _crr ((p/M_c)PE(M_c/p))^2/3 against log (a_T γ^s _cr), where a_T is the WLF shift factor, M_c the molecular weight between entanglements and p the density.

Estimation of slip rates at the wall and measurements on slightly crosslinked high density polyethylene supports the assumption that spurt results from melt fracture at the capillary wall.

Only addition of the non-solvent calcium stearate (with high density polyethylene) results in flow behavior which significantly deviates from that found for samples containing good solvents. Gel permeation chromato-graphy indicates that if chain scission resulting in lower molecular weight takes place, it will be limited to thin layers near the capillary wall.

melt fracture in the capillary cannot be reached. The flow behavior is influenced by addition of the non-solvent calcium stearate. The slopes of the flow curves is changed at relatively low shear rates but the high molecular weight polymer DMDS 5140 never the less shows spurt behavior at the same stress as for the pure sample.

This behavior may tentatively be interpreted as being caused by the formation of a boundary layer of non-solvent at low shear rate the thickness of which depends on the polymer and flow field. At stresses corresponding to the critical conditions, fracture in the polymer takes place. The interface between the non-solvent layer and the polymer matrix must according to Han61 be expected to be unstable     

Processing and room temperature mechanical properties of a zirconium carbide ceramic

Zirconium carbide (ZrC) powder, batched to a ratio of 0.98 C/Zr, was prepared by carbothermal reduction of ZrO₂ with carbon black. Nominally phase-pure ZrC powder had a mean particle size of 2.4 μm. The synthesized powder was hot-pressed at 2150°C to a relative density of > 95%. The mean grain size was 2.7 ± 1.4 μm with a maximum observed grain size of 17.5 μm. The final hot-pressed billets had a C/Zr ratio of 0.92, and oxygen content of 0.5 wt%, as determined by gas fusion analysis. The mechanical properties of ZrC_0.92O_0.03 were measured at room temperature. Vickers’ hardness decreased from 19.5 GPa at a load of 0.5 kgf to 17.0 GPa at a load of 1 kgf. Flexural strength was 362.3 ± 46 MPa, Young's modulus was 397 ± 13 MPa, and fracture toughness was 2.9 ± 0.1 MPa•m^1/2. Analysis of mechanical behavior revealed that the largest ZrC grains were the strength-limiting flaw in these ceramics.     

Mechanical behavior of electrophoretically modified CFRP composites at elevated temperatures: An assessment of the influence of graphene carboxyl bath concentration

The study aims at investigating the mechanical behavior of carbon fiber reinforced polymer (CFRP) composites modified with graphene carboxyl at elevated temperature (ET-110°C) and understanding the effect of electrophoretic deposition bath concentration (0.5 g/L, 1.0 g/L, and 1.5 g/L) on their mechanical behavior at ET. The 1.5 g/L composite has revealed a maximum improvement in energy absorbed before failure of 33.25% at RT and 22.54% at ET for flexural testing and ∼35% at RT for short beam shear testing, over neat CFRP composite. The modified composites have shown an improved flexural strain to failure at both RT and ET, with 1.5 g/L composite exhibiting maximum enhancement of 12.41% at RT and 26.52% at ET over neat composite. However, at ET, modified composites exhibited lower flexural strength and interlaminar shear strength values in comparison to that of neat. Viscoelastic behavior of all composites was studied to understand bath concentration's effect on thermal behavior via dynamic mechanical thermal analysis. Differential scanning calorimetry was employed for governing the glass transition temperature of composites. Fractography of tested samples (both ET and RT) was performed utilizing a scanning electron microscope to determine the prominent failure mode.     

Stretching of self-interacting wormlike macromolecules

Structural and elastic properties of non-charged polymers of stiffness ranging from flexible to rigid chains are computed by Monte Carlo simulations. A discrete wormlike chain (WLC) model with self-interacting units is applied to chains of intermediate lengths of interest in the AFM measurements. Variations of the persistence length and mean chain dimensions with bending stiffness are presented. The chain-end distribution functions, the Helmholtz elastic energy and the force-extension profiles of chains of variable stiffness are computed in an isometric ensemble. Occurrence of a plateau on the force-extension curves at intermediate chain stiffness is noted. Qualitative differences are found between force profiles from simulations and from the standard (ideal) WLC model. The differences can be ascribed to an inherent dissimilarity between isometric and isotensional ensembles used and, at small extensions, to the excluded-volume effects. The single-chain functions from simulations were employed to investigate the influence of bending stiffness on elasticity of networks of semiflexible chains by the three-chain model. A stark reduction of degree of elongation of a network with rising stiffness is found. Stress-strain relations show a highly non-linear behavior with the marked strain-stiffening effect.     

Dry-sliding wear behavior of 3Y-TZP/Al2O3-NbC nanocomposites produced by conventional sintering and spark plasma sintering

This work presents the initial results of the dry-sliding wear behavior of 3 mol% yttria-stabilized zirconia reinforced with 5 vol% alumina-niobium carbide (3Y-TZP/5 vol% Al₂O₃-NbC) nanocomposites sintered by conventional sintering and spark plasma sintering methods in the temperature range of 1350-1450°C. The reinforcement of 3Y-TZP matrix with hard nanoparticles aimed to improve wear strength of the composites. Wear tests were performed by the ball-on-disc method using alumina (Al₂O₃) and tungsten carbide with 6 wt% cobalt cermet (WC-6%Co) balls as counter-materials, a load of 15 N, a sliding distance of 2000 m, and a sliding speed of 0.1 m/s. Wear behavior was evaluated in terms of wear rate and FE-SEM micrograph analysis of the wear tracks. The nanocomposite sintered at 1450°C by conventional sintering exhibited the least wear when tested with the WC-6%Co ball. Generally, the wear mechanism showed evidence of severe wear regime with both counter-materials.     

An investigation of phosphate based ECMP electrolyte performance on feature scale planarization

Conventional copper chemical mechanical planarization (CMP) techniques are being pushed to their limits by increasing industrial standards caused by device miniaturization and the use of new materials. There is a need to investigate alternative methods of polishing to maintain and/or improve planarization standards while operating at low downforce. In this study, electrochemical mechanical planarization (ECMP) is considered as an alternative and/or an extension to current CMP processes. ECMP is unique due to the combination of an applied voltage to oxidize Cu and an abrasion from a polishing pad, which potentially allows the system to achieve high levels of planarization through the use of an appropriately tailored electrolyte. An electrolyte containing 1.0 M potassium phosphate salt concentration with a pH value of 2 and a benzotriazole (BTA) concentration of 0.001 M was tested for its planarization capability on patterned Cu structures using a custom built ECMP tool. Feature sizes of the Cu structures were varied from 1 to 6 μm. Similar planarization results were achieved using three pad types. All experiments were performed at 0.5 V versus Ag/AgCl reference. The average step height reduction (SHR) was ~840 nm while the decrease in the average metal thickness removed (λ_avg) was on the order of ~430 nm. Because features were approximately 50% of the substrate area, the total average metal thickness removed was approximately half of the SHR for all three pad types.     

Structure analysis and electrical properties of 10PbTiO3─10Fe2O3─30V2O5─50B2O3 via high energy mechanochemical technique

A non-conventional mechanochemical processing technique was used to prepare fine-grain of mixed iron and vanadium oxides with a lead titanate system at boron oxide matrix. The structures of the ball milled samples were analyzed at different milling times and temperatures. After 30h of mechanical milling, the vanadium peaks completely disappeared, and partially supersaturated solid solution was formed. The average crystallite size of the 30h milled sample calculated from XRD patterns decreases rapidly from 3.72 μm to 69.4 nm while the crystallite size of the 50h was 26.3 nm. The DSC curve confirms the mechanochemical reactions. Metastable phases of lead vanadium oxide obtained after heat treatment with average crystallite size 65 nm in a non-crystalline matrix. The conductivity of the heat-treated samples increases with increasing heating temperature. The conductivity of all the prepared samples was found to be consistent with small polaron hopping, Mott’s theory which confirmed by studying the power law behavior of its AC conductivity. The AC conductivity increases with increasing temperature and frequency.     

Fabrication and properties of highly transparent Tm3Al5O12 (TmAG) ceramics

Highly transparent Tm₃Al₅O₁₂ (TmAG) ceramics were fabricated by solid-state reaction and vacuum sintering. Densification, microstructure evolution, mechanical, thermal, and optical properties of the TmAG ceramics were investigated. Fully dense TmAG ceramic with average grain size of 15 μm was obtained by sintering at 1780 °C for 20 h. The in-line transmittance was 80.5% at 2000 nm. The absorption coefficients at 682 nm and 785 nm were 8.03 cm⁻¹ and 8.33 cm⁻¹, respectively. The Vickers hardness, the Young modulus, the bending strength, and the fracture toughness values were 15.14 GPa, 343 GPa, 230 MPa, and 2.35 MPa m^1/2, respectively. The thermal conductivity at room temperature was 3.3 W/m K and the average linear thermal expansion coefficient from 20 °C to 1000 °C was 8.915 × 10⁻⁶ K.     

Influence of the synthesis conditions on the properties of thermoplastic polyurethane elastomers

Thermoplastic polyurethane elastomers (TPUs) of constant composition were prepared by using the prepolymer method and by changing the reaction conditions (prepolymerization and chain‐extension time) to study the influence of these conditions on the final TPU properties. The TPUs were characterized by gel permeation chromatography, differential scanning calorimetry, strain–stress measurements, and contact‐angle measurements. To test the adhesion properties of the TPUs, poly(vinyl chloride) strips were bonded to each other by using TPU solutions and the T‐peel strength of the adhesive joints was measured. It was found that provided a threshold is crossed, the prepolymerization time markedly influences the final properties of the TPUs (viscosity of solutions, molecular weight, mechanical and adhesive behavior), whereas the chain extension time does not. Therefore, it is possible to prepare TPUs with specific properties by playing with the prepolymerization conditions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1590–1595, 2000     

A novel design for water-based modified epoxy coating with anti-corrosive application properties

In this study, a polysulfide rubber emulsion was synthesized through the pre-emulsification of polysulfide rubber by mixed-emulsifiers and polyvinyl alcohol as a weight stabilizer and the emulsification by adding deionized water dropwise at a speed of 1 ml/min, stirring at a speed of 1500 rpm and adjusting pH to 8 by ammonia. The epoxy coating was modified by the polysulfide rubber emulsion. The anticorrosive coating was prepared by using waterborne amine dispersion as a curing agent and polysulfide rubber as a modifier. It had a good chemical resistance and excellent overall mechanical performance. The coatings were characterized by Tafel polarization curves and Scanning electron microscope.