Emulsion Polymerized Polystyrene/Montmorillonite Nanocomposite and its Viscoelastic Characteristics

A novel polystyrene (PS)/clay nanocomposite was synthesized using a simple emulsion polymerization method in the presence of sodium ion exchanged montmorillonite (Na‐MMT). Prior to the radical polymerization procedure with potassium persulfate (KPS) as an initiator, the hydrophobic styrene monomer was intercalated into hydrophilic clay layers using sodium dodecyl sulfate (SDS) as a surfactant. The FTIR spectra of the products showed the characteristic absorbance peaks of both the synthesized PS and Na‐MMT. The x‐ray diffraction patterns of the products exhibited an increase in the d ₀₀₁‐spacing, pointing to the intercalation of the PS chains into the intergalleries of the Na‐MMT. The enhancement of the thermal properties of the nanocomposite materials, such as the increase in the glass transition temperature of the PS, was investigated by differential scanning calorimetry (DSC). Furthermore, based on the viscoelastic properties of the products examined using a rotational rheometer with a parallel plate geometry, the nanocomposites were found to exhibit more rapid shear thinning and increased storage (G′) and loss (G″) moduli with increasing clay content.     

Preparation and properties of polyurethane/MMT nanocomposite actuators

This study dealt with the electrostrictive response of a polyurethane (PU)/clay nanocomposite film, which was a promising candidate for a material to be used in polymer actuators. The nanocomposites were produced by using three types of montmorillonites (MMTs) such as natural MMT (Cloisite^®Na⁺), hydrophobic MMT (Cloisite^® 20A), and hydrophilic MMT (Cloisite^® 30B). The nanometer-scale silicate layers of organo-clay were completely exfoliated in PU for the cases of 1, 3 and 5 wt% PU/MMT nanocomposites as confirmed by wide X-ray diffraction (WAXD) profiles. Actuation tests indicated that the displacement of PU/MMT nanocomposite actuator was larger than pure PU actuator, caused by an increase in dielectric constant. Especially, PU/MMT nanocomposite actuator with Cloisite^® 30B had the largest displacement and it became possible to operate at low voltage.     

Epoxy-organoclay nanocomposites: morphology,moisture absorption behavior and thermo-mechanical properties

The morphology and moisture barrier characteristics are studied of epoxy-based nanocomposites reinforced with layered silicates. Two different types of organoclay, including the quaternary alkylamine modified montmorillonite (KH-MT) and the octadecylamine modified montmorillonite (I30P), were studied. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that the I30P system exhibited a large increase in interlayer d -spacing from 3.39 mm to over 8 nm during the curing process, whereas the KH-MT system showed negligible changes in reflection angle and d -spacing, with the final interlayer distance of 3.39 nm after cure. The moisture absorption behaviour was different for different organoclays: the moisture absorption rate was similar for the neat polymer and the KH-MT system, which could be fitted to Fick's second law. The moisture absorption rate of the I30P system was much lower than the two systems, which was predicted using a non-Fickian model based on the ID Langmuirian solution. The deviation from the Fickian diffusion for the latter system is associated with exfoliated morphology and more uniform dispersion of clay particles, which altered the diffusion path of water molecules in the nanocomposite. The moisture diffusivity of nanocomposites in general decreased with increasing clay content, the reduction being more pronounced for the I30P system. The normalized permeability also showed a systematic degradation with increasing clay content, which agrees well with the prediction based on the tortuous path model.     

Carbon nanotube/polyaniline nanocomposites and their electrorheological characteristics under an applied electric field

A conducting polyaniline (PANI) was synthesized via an oxidative dispersion polymerization technique, using poly(vinyl alcohol) (PVA) as a polymeric stabilizer, in the presence of multi-walled carbon nanotubes (MWNT) purified in acidic solution, and dispersion stability of the MWNT in an aqueous solution of PVA was studied for different PVA concentrations. Their morphology was confirmed by a scanning electron microscope. Its electrorheological (ER) characteristics were also investigated by dispersing the PANI/MWNT composite particles in an insulating silicone oil. Its ER properties were examined using a rotational rheometer under varying applied DC electric field strengths, in which the ER fluid is generally composed of a suspension of conducting particles dispersed in an insulating fluid, which shows a rapid and reversible change in shear viscosity with an applied electric field. Synthesized PANI/MWNT composite particles are observed to enhance interparticular interactions, since the degree of polarization of PANI/MWNT composite particle increases with applied electric field strengths. The shear stresses of the PANI/MWNT nanocomposite based ER fluid increase with the electric field strength for a broad range of shear rates.     

Two-nozzle electrospinning of (MWNT/PU)/PU nanofibrous composite mat with improved mechanical and thermal properties

Composite nanofibrous mat composed of neat polyurethane (PU) and multiwalled carbon nanotubes/polyurethane (MWNT/PU) nanofibers have been fabricated by one-step angled two-nozzle electrospinning. The morphological, thermal, and mechanical properties of the electrospun nanofibers were evaluated. The diameters of electrospun neat PU and composite nanofibers ranged from 239 to 1058 nm. The two-nozzle electrospun (MWNT/PU)/PU composite nanofibers showed curly, and randomly-oriented fibers with interfiber bonding, and were generally bigger in size than single-nozzle electrospun nanofibers. The tensile strength of the neat PU composite nanofiber mat obtained from two-nozzle electrospinning was 25% higher than that obtained from neat PU single-nozzle electrospinning. The incorporation of MWNTs in the composite nanofiber increased the tensile strength by as much as 64% without reducing elongation, made the composite nanofiber more thermally stable, and improved the melting zone. The present results showed that side-by-side angled two-nozzle electrospinning can improve the quality of the electrospun nanofibers that could have potential application in different fields such as filtration, protective clothing and tissue engineering.     

Synthesis and Properties of Polyacrylamide-Based Conducting Gels with Enhanced Mechanical Strength

A nanocomposite conducting hydrogel, polyacrylamide/MWNT/clay (abbreviated as PAM/MWNT/clay), prepared through in situ free radical aqueous polymerization and crosslinked by both clay, as a functional physical crosslinker, and N,N′-methylenebisacrylamide (MBA) as a chemical crosslinker, is reported. The morphology of the gels was characterized by scanning electron microscopy (SEM). The mechanical properties and electrical conductivity were also studied. The results show that the prepared hydrogels had the expected chemical components, with a highly porous structure, and the gels also showed high mechanical strength. The mechanical strength and electrical conductivity value increased with increasing content of multi-walled nanotube (MWNT), and decreased with increasing content of water.     

Structure and Properties of a cis-1,4-Polybutadiene/Organic Montmorillonite Nanocomposite Prepared via In Situ Polymerization

Cis-1,4-polybutadiene (cis-1,4-PB) is one of the most important synthetic rubbers, having superior performances such as wear resistance, cold resistance and high elasticity. However, its mechanical properties, including low tensile strength, tear resistance and thermal stability, limit its application in comparison to natural rubber and butadiene-styrene rubber that have excellent overall performances. Thus, the reinforcing of cis-1,4-PB is a necessity. The dispersion of clay in rubbers on the nanoscale can improve the mechanical, gas permeability and thermal properties of the resulting composites. In this paper, organic montmorillonite (OMMT) clay was dispersed into the cis-1,4-PB matrix via an in-situ polymerization method and the chemical structure, phase morphology, mechanical properties and thermal stability of the composite were investigated. The properties of the composite were analyzed by such techniques as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA). In the in-situ polymerization, a Ni-based catalyst system with the presence of OMMT showed high efficiency and 1,4-selectivity for the polymerization of butadiene. The OMMT could be dispersed in the polymeric matrix on the nanoscale during the polymerization. The interfusion of OMMT had little influence on the thermal stability and the chemical micro-structure of the cis-1,4-PB when the content of cis-1,4 units was more than 95%. The loss tangent of the composite was higher than that of cis-1,4-PB from ?110 to ?55°C, the temperature range examined, and the mechanical properties of the cis-1,4-PB/OMMT nanocomposite (NC) were improved upon the addition of OMMT.     

Synthesis and characterization of polyurethane/SiO2 nanocomposites

In order to achieve good dispersion of nano-SiO₂ and increase the interactions between nano-SiO₂ and PU matrix, nano-SiO₂ was firstly modified with poly(propylene glycol) phosphate ester (PPG-P) which was a new polymeric surfactant synthesized through the esterification of poly(propylene glycol) (PPG) and polyphosphoric acid (PPA). Then a series of polyurethane (PU)/SiO₂ nanocomposites were prepared via in situ polymerization. The surface modification of nano-SiO₂, the microstructure and the properties of nanocomposites were investigated by FTIR, SEM, XRD and TGA. It was found that good dispersion of nano-SiO₂ achieved in PU/SiO₂ nanocomposite after the modification with PPG-P. The segmented structures of PU were not interfered by the presence of nano-SiO₂ in these nanocomposites.     

Preparation,Characterization and Coreflood Investigation of Polyacrylamide/Clay Nanocomposite Hydrogel System for Enhanced Oil Recovery

The synthesis and characterization of polyacrylamide/clay nanocomposites for the development of hydrogel system used in enhanced oil recovery is described. The synthesized nanocomposite copolymer was crosslinked with Chromium (III) acetate to form the hydrogel which exhibited an acceptable gel strength, gelation time and gel stability. The nanocomposite gels prepared with low crosslinker concentration (2000 ppm chromium acetate) showed higher gel strength and required longer gelation time than the conventional polyacrylamide (PAAm) gel; these are desirable properties for the effective placement of gel during enhanced oil recovery operations. The effects of various parameters, such as polymer and crosslinker concentration, on the gelation time and gel strength were evaluated using the bottle testing method. X-ray diffraction (XRD) and field-emission scanning electron microscopy (FESEM) revealed the formation of intercalated and exfoliated clay morphologies. The effects of the clay content on the thermal stability and gel strength of the gel network were also investigated by thermogravimetric analysis (TGA) and rheological measurements (oscillatory time sweep profiles), respectively. Also, in-situ gelation and core flooding experiments revealed that a significant permeability reduction of the sand pack cores could be achieved at reservoir conditions when they were treated with the developed nanocomposite gel formulation. Hence, this nanocomposite gel system with low crosslinker concentration (10,000 ppm of nanocomposite polymer concentration containing 2000 ppm of clay with 2000 ppm chromium acetate crosslinker) may be suitable in water shut-off treatments required for enhanced oil recovery from the oil fields.     

超微镍粒子/聚苯胺纳米复合材料制备及其表征

反相微乳液法 (inversemicroemulsionsystems ,W /O型 )是制备纳米复合材料有效而简单的液相化学制备方法[1,2 ] .本工作首次采用两步连续反相微乳液法原位聚合制备超微镍粒子 (Ni) /聚苯胺 (PANI)纳米复合材料 .首先 ,利用无机化合物之间的氧化还原反应 ,将十二烷基苯磺酸钠 (DBS)和NiCl2 溶液按一定比例加入锥形瓶中 ,再加入异戊醇和正庚烷混合溶剂 ,常温下电磁力搅拌 ,体系变得半透明 (淡黄色 )形成微乳溶液 (W /O型 )称为 (A) ;然后再配制DBS和NaBH4 与异戊醇和正庚烷混合溶剂 ,形成微乳溶液 (W /O型 )称为 (B) ;两步连续反相…     

In situ monitoring of styrene polymerization using Raman spectroscopy. Multi‐scale approach of homogeneous and heterogeneous polymerization processes

Free radical polymerization of styrene was monitored in situ by combining Raman spectroscopy to other experimental techniques (gravimetry and rheology). Three different processes were investigated: bulk, emulsion and miniemulsion polymerization. A complete analysis of the evolution of Raman spectrum during the course of reaction showed that a lot of information about molecular dynamics could be extracted and related to chemical phenomena. In addition, we report for the first time the coupling of Raman spectroscopy to a rheometer in order to monitor styrene bulk polymerization both at the scale of chemical bonds and at the scale of macroscopic phenomena (viscosity variation). Copyright © 2013 John Wiley & Sons, Ltd.     

Cyclopentane hydrate slurry viscosity measurements coupled with visualisation

One of the advanced strategies in hydrate plug prevention is to obtain an in-depth knowledge of the rheological properties of hydrate slurries. A major challenge in hydrate rheological measurements is that the viscosity profile can be difficult to attribute to physical phenomena, such as particle agglomerate breakup, particle bedding/settling and wall growth. In this work, a novel visual rheometer has been developed to help overcome these previous limitations by enabling the visualisation of the evolution of cyclopentane hydrate slurries during viscosity measurements. Two different model systems were used in this investigation: (1) non-emulsified and (2) emulsified systems. The physical phenomena, including initial hydrate formation, hydrate wall growth, bedding and sloughing were visually observed and directly correlated to the corresponding viscosity profile. For the non-emulsified system, there are four different stages of hydrate slurry development including initial hydrate formation, wall adhesion and growth and sloughing that caused changes in the viscosity profiles. Large fluctuations in the viscosity profile for a non-emulsified system were found to be the result of a sloughing phenomenon. On the other hand, the emulsified system showed a well-dispersed hydrate slurry with minimal wall and impeller growth, corresponding to a smooth viscosity profile.     

Preparation and Rheological Characteristics of Ethylene‐Vinyl Acetate Copolymer/Organoclay Nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) with 40 wt.% vinyl acetate content (EVA40)/organoclay nanocomposites were prepared using a melt intercalation method with several different clay concentrations (2.5, 5.0, 7.5, and 10.0 wt.%). X‐ray diffraction confirmed the formation of exfoliated nanocomposite in all cases with disappearance of the characteristic peak corresponding to the d‐spacing of the pristine organoclay. Transmission electron microscopy studies also showed an exfoliated morphology of the nanocomposites. Morphology and thermal properties of the nanocomposites were further examined by means of scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA), respectively. Rheological properties of the EVA40/organoclay nanocomposites were investigated using a rotational rheometer with parallel‐plate geometry in both steady shear and dynamic modes, demonstrating remarkable differences with the clay contents in comparison to that of pure EVA40 copolymer.     

Dynamic Rheology of Poly(3-hydroxybutyrate-co-4-Hydroxybutyrate) /Clay Biocomposites

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] composites filled with clay were prepared by a melt blending process. Dynamic rheology of the composites was measured by means of a rotational rheometer. The results showed that the interlayer spacing of the clay increased owing to the presence of the P(3HB-co-4HB) melt in the interlayer regions of the clay. The storage and the loss moduli of the composite samples increased with the increasing frequency, and decreased with the increasing temperature. The addition of the clay enhanced the oscillatory thinning behavior of the composite melts, and improved the processability of the P(3HB-co-4HB) melt. The decrease of the viscosity by increasing both frequency and temperature was feasible and effective for the composites with the clay contents of 1 and 2 wt.%.     

Structure and Mechanical Properties of 50/50 NR/SBR Blend/Pristine Clay Nanocomposites

A blend/clay nanocomposites of 50/50 (wt%) NR/SBR was prepared via mixing the latex of a 50/50 NR/SBR blend with an aqueous clay dispersion and co‐coagulating the mixture. The structure of the nanocomposite was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Nanocomposites containing less than 10 phr clay showed a fully exfoliated structure. After increasing the clay content to 10 phr, both nonexfoliated (stacked layers) and exfoliated structures were observed in the nanocomposites. The results of mechanical tests showed that the nanocomposites presented better mechanical properties than clay‐free NR/SBR blend vulcanizate. Furthermore, tensile strength, tensile strain at break, and hardness (shore A) increased with increasing clay content, up to 6 phr, and then remained almost constant.     

On the Thermal Degradation of a Novel Epoxy-Based Nanocomposite Cured With Tryptophan as an Environment-Friendly Curing Agent

The thermal degradation kinetics of diglycidyl ether of bisphenol-A (DGEBA) cured with tryptophan (Trp) in the presence of silica nanoparticles (SiNP) was investigated by thermogravimetry analysis. The activation energies of the solid-state decomposition process were evaluated using the advanced isoconversional method. The dependence of conversion (degradation) on the temperature and activation energy was determined allowing the calculation of master plots. The experimental master plots agreed with the first-order (F1) kinetic function for both neat epoxy and nanocomposite in the conversion range of 0.45–0.85. Using the kinetic model and the calculated kinetic parameters, the times at half conversion (α = 0.5) were computed for different degradation temperatures. The kinetic analysis showed that the degradation rate of the epoxy nanocomposite was lower than that of the neat epoxy for conversions between 0.45 and 0.85. Therefore, we concluded that adding SiNP to DGEBA/Trp can improve the thermal stability in the conversion range of 0.45–0.85.     

Nonisothermal Crystallization of the Polypropylene/Organosilica Nanocomposite

Abstract

Nonisothermal crystallization of the neat isotactic polypropylene homopolymer (PP‐0) and of the nanocomposite containing 4.68 wt.% of organosilica (PP‐4.68) was studied in the standard differential scanning calorimetry (DSC) mode during constant‐rate cooling from the melt state. Analysis of the nucleation parameters derived from cooling rate dependencies of the temperatures for the onset of crystallization exotherms suggested a slight increase of the nucleation barrier for lamellar crystallization of PP within a confined space between neighboring nanoparticles of an infinite cluster of the nanocomposite, concomitant to stronger restrictions to transport of PP segments across the melt/lamellar crystal interface. The overall crystallization rate data for PP‐4.68 were consistent with the assumption of two separate contributions from the initial (unconstrained) and the subsequent (constrained) nucleation mechanisms, respectively. The obtained results were considered as evidence for a coexistence in an undercooled PP melt of the nanocomposite of initial nucleation sites characteristic for the neat PP‐0, and the basically different nucleation sites (presumably, PP chains anchored by both ends to the surfaces of two adjacent nanoparticles).     

On Localization of Clay Nanoparticles in Polypropylene/poly(Lactic Acid) Blend Nanocomposites: Correlation with Mechanical Properties

Two polypropylene (PP)/polylactide (PLA)/clay ternary nanocomposite systems, i.e. PP-rich and PLA-rich ones, each containing various amounts of one of two types of clay, were prepared by one step melt compounding in a twin screw extruder. The microstructures of the developed systems were correlated with tensile and impact properties. A theoretical calculation using wetting coefficients was used for predicting the clay nanoparticles localization in the blends. The nanoparticles were almost completely located within the PLA phase in both the PP-rich and PLA-rich systems, in good agreement with the predictions. Addition of a compatibilizer led to localization of the nanoparticles at the interfaces of the blends. From the wide angle X-ray scattering (WAXS) spectra it was concluded that the incorporation of clay led to intercalated structures in the both systems. The increase in impact toughness of the compatibilized blend nanocomposites, with respect to the uncompatibilized ones, was attributed to the weakened interfacial debonding in the presence of the interfacial-localized nanoparticles.     

Fabrication and Physical Characterization of Biodegradable Poly(butylene succinate)/Carbon Nanofiber Nanocomposite Foams

Nanocomposites of biodegradable poly(butylene succinate) (PBS) and carbon nanofibers (CNFs) were prepared by three different methods, that is, solution blending, melt compounding, and solution and subsequent melt blending (SOAM) method, among which the SOAM method, where nano-scale fillers and polymer matrix are solution-blended and subsequently melt-mixed in a torque rheometer, is a two-step process for obtaining polymer nanocomposite. Dispersion of CNFs in the PBS matrix was characterized by FE-SEM, while thermal and mechanical properties were analyzed by thermogravimetric ananlysis (TGA) and universal test machine (UTM), respectively. The PBS/CNF nanocomposites were then converted to foams by employing a chemical blowing agent (CBA) in the melt. The presence of CNFs increased the melt viscosity of PBS so that the PBS/CNF nanocomposite foams were produced without modifying the chemical structure of the PBS. Nanocomposite foams prepared by the SOAM method showed higher physical properties compared with those prepared by the solution blending and the melt mixing. Cell size and blowing ratio increased with the increase in the CBA content, blowing temperature and time. Cell morphology of the nanocomposite foams was examined by optical microscopy, and the cell size distribution was also investigated.     

Rheology,Crystallization, Mechanical and Barrier Properties of Polyamide 6/66 Nanocomposites with Exfoliated Organoclays

Nylon copolymer/clay (NC) nanocomposites were prepared using PA6/66 as a matrix and organoclay as a nanofiller through a two-step melt-compounding method. It was shown that the organoclay flakes were well exfoliated and dispersed in the PA6/66 matrix. With increasing content of organoclay, the apparent shear viscosity and the entrance pressure drop of the NC nanocomposites decreased whereas the corresponding shear activation energy increased, suggesting that the NC nanocomposites were suitable to be used in shear-flow rather than extension-flow related processes. Investigations of the crystallization behaviors of the NC nanocomposites indicated that the organoclay addition was capable of facilitating the γ-form crystal formation, which is suggested to be due to the restriction effect of the organoclay on the PA6/66 chain motion during the crystallization. Compared to the neat PA6/66, the tensile strength and elongation at break of the NC nanocomposites were both enhanced at an appropriate content of the organoclay. In addition, the NC nanocomposites exhibited enhanced barrier properties due to the high specific surface area and the homogeneous dispersion of the organoclay.