Calculating the equation of state parameters and predicting the spinodal curve of isotactic polypropylene/poly(ethylene-co-octene) blend by molecular dynamics simulations combined with Sanchez-Lacombe lattice fluid theory

Molecular dynamics simulations are adopted to calculate the equation of state characteristic parameters P*, rho*, and T* of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOC), which can be further used in the Sanchez-Lacombe lattice fluid theory (SLLFT) to describe the respective physical properties. The calculated T* is a function of the temperature, which was also found in the literature. To solve this problem, we propose a Boltzmann fitting of the data and obtain T* at the high-temperature limit. With these characteristic parameters, the pressure-volume-temperature (PVT) data of iPP and PEOC are predicted by the SLLFT equation of state. To justify the correctness of our results, we also obtain the PVT data for iPP and PEOC by experiments. Good agreement is found between the two sets of data. By integrating the Euler-Lagrange equation and the Cahn-Hilliard relation, we predict the density profiles and the surface tensions for iPP and PEOC, respectively. Furthermore, a recursive method is proposed to obtain the characteristic interaction energy parameter between iPP and PEOC. This method, which does not require fitting to the experimental phase equilibrium data, suggests an alternative way to predict the phase diagrams that are not easily obtained in experiments.

Suppression of phase separation in PC/PMMA blend film by thermoset oligomer

Phase separation of bisphenol A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) thin blend film is suppressed by addition of solid epoxy oligomer. Epoxy has strong intermolecular interactions with both PC and PMMA, while PC and PMMA are quite incompatible with each other. Consequently, phase separation in the PC/PMMA blend film pushes epoxy to the interface; at the same time, PC and epoxy react readily at the interface to form a cross-linking structure, binding PMMA chains together. Therefore, the interface between PC and PMMA is effectively reinforced, and the PC/PMMA thin blend film is stabilized against phase separation. On the other hand, only an optimal content of epoxy (i.e., 10 wt %) can serve as an efficient interfacial agent. In contrast to the traditional reactive compatibilization, here we observed that the cross-linking structure along the interface is much more stable than block or graft copolymers. Atomic force microscopy (AFM) is used to characterize the morphological changes of the blend films as a function of annealing time. Two-dimensional fast Fourier transform (2D-FFT) of AFM data allows quantitative investigation of the scaling behavior of phase separation kinetics.

Electrostatic interaction hybrids from water-borne conductive polyaniline and inorganic precursor containing carboxyl group

Electrostatic interaction conductive hybrids were prepared in water/ethanol solution by the sol-gel process from inorganic sol containing carboxyl group and water-borne conductive polyaniline (cPANI). The electrostatic interaction hybrids film displayed 1-2 orders of magnitude higher electrical conductivity in comparison with common hybrids film, showing remarkable conductivity stability against water soaking. Most strikingly, it displayed ideal electrochemical activity even in a solution with pH = 14, which enlarged the conducting polyaniline application window to strong alkaline media.

Water-resistant conducting hybrids from electrostatic interactions

Conductive hybrids were prepared in a water/ethanol solution via the Solgel process from an inorganic sol containing carboxyl groups and water-borne conductive polyaniline (cPANI). The inorganic sol was prepared by the hydrolysis and condensation of methyltriethoxysilane with the condensed product of maleic anhydride and aminopropyltriethoxysilane as a catalyst, for which the carboxyl counterion along the cPANI backbone acted as an electrostatic-interaction moiety. The existence of this electrostatic interaction could improve the compatibility of the two components and contribute to the homogeneous dispersion of cPANI in the silica phase. The electrostaticinteraction hybrids displayed a conductivity percolation threshold as low as 1.1 wt % polyaniline in an emeraldine base, showing 2 orders of magnitude higher electrical conductivity than that without electrostatic interactions. The electrostatic-interaction hybrids also showed good water resistance; the electrical conductivity with a cPANI loading of 16 wt % underwent a slight change after 14 days of soaking in water.

Conductive hybrid film from polyaniline and polyurethane-silica

In order to improve the mechanical performance and water resistance of water-borne conducting polyaniline film, conducting polyaniline/polyurethane-silica hybrid film was prepared in aqueous solution employing silanol-terminated polyurethane and methyltriethoxysilane as sol-gel precursors. The hybrid film showed surface resistivity of 10(8) Omega even though the conducting polyaniline loading was only 10 wt% (or 1.5 wt% of polyaniline), and the mechanical performance as well as water resistance was significantly improved, making it suitable for antistatic application. Therefore, a practical route to water-borne processing of conducting polyaniline is disclosed.

Online study of the formation of PA6 droplets in PP matrix under shear flow

Breakup process of polyamide 6 (PA6) in polypropylene (PP) matrix under shear flow was online studied by using a Linkam CSS 450 stage equipped with optical microscopy. Both tip streaming and fracture breakup modes of PA6 droplets were observed in this study. It was reported that the droplet would break up by tip streaming model when the radio of the droplet phase viscosity to the matrix phase viscosity (n(r) = n(d)/n(m)) is smaller than 0.1 (Taylor, Proc R Soc London A 1934, 146, 501; Grace, Chem Eng Commun 1982, 14, 225; Bartok and Mason, J Colloid Sci 1959, 14, 13; Rumscheidt and Mason, J Colloid Sci 1961, 16, 238; de Bruijn, Chem Eng Sci 1993, 48, 277). However, the tip streaming model was observed even when the viscosity ratio was much greater than 0.1 (n(r) = 1.9). In this study for the tip streaming mode, small droplets were ruptured from the tip of the mother droplet. On the other hand, the mother droplet was broken into two or more daughter droplets with one or several satellite droplets between them for the fracture mode. It was found that PA6 droplet was much elongated at first, and then broke up via tip streaming or fracture to form daughter droplets or small satellite droplets with the shape of fiber or ellipse.

Study of hydrogen-bonded blend of polylactide with biodegradable hyperbranched poly(ester amide)

Polylactide (PLA) was melt blended with a biodegradable hyperbranched poly(ester amide) (HBP) to enhance its flexibility and toughness without sacrificing comprehensive performance. The advantage of using HBP was due to its unique spherical shape, low melt viscosity, and abundant functional end groups together with its easy access. Rheological measurement showed that blending PLA with as little as 2.5% HBP resulted in a 40% reduction of melt viscosity. The glass transition temperature (T-g) of PLA in the blends decreased slightly with the increase of HBP content, indicating partial miscibility which resulted from intermolecular interactions via H-bonding. The H-bonding involving CO of PLA with OH and NH of HBP was evidenced by FTIR analysis for the first time. The HBP component, as a heterogeneous nucleating agent, accelerated the crystallization rate of PLA. Remarkably, with the increase of HBP content, the elongation at break of PLA blends dramatically increased without severe loss in tensile strength, even the tensile strength increased within 10% content of HBP. The stress-strain curves and the SEM photos of impact-fractured surface showed the material changed from brittle to ductile failure with the addition of HBP. Reasonable interfacial adhesion via H-bonding and finely dispersed particulate structure of HBP in PLA were proposed to be responsible for the improved mechanical properties.

A Monte Carlo simulation of morphology and structure for thin films of symmetric triblock copolymer after quenching and annealing

Self-assembly thin films of symmetric triblock copolymer after annealing and quenching were examined by an effective Monte Carlo simulation method. The defects in the ordered lamellae of the thin films after quenching, which were dependent on the initialization of copolymer melts, are removed in the thin films after annealing. The mean-square gyration radius and end-to-end distance of copolymer chains in the thin films after annealing are smaller than those in the thin films after quenching because of the complete relaxation of polymer during annealing. We also find that the density of A block in the region near to the surface is higher than that in the interior of the thin films. As a result, it is different from the thin films of symmetric A(n)B(n) diblock copolymer, in which surface ordering forms before the interior, that ordering phenomena occurs first in the interior region in the thin films of symmetric A(n)B(m)A(n). triblocl copolymer.

Independence of the brittle-ductile transition from the rubber particle size for impact-modified poly(vinyl chloride)

A series of acrylic impact modifiers (AIMS) with different particle sizes ranging from 55.2 to 927.0 nm were synthesized by seeded emulsion polymerization, and the effect of the particle size on the brittle-ductile transition of impact-modified poly(vinyl chloride) (PVC) was investigated. For each AIM, a series of PVC/AIM blends with compositions of 6, 8, 10, 12, and 15 phr AIM in 100 phr PVC were prepared, and the Izod impact strengths of these blends were tested at 23 degrees C. For AIMs with particle sizes of 55.2, 59.8, 125.2, 243.2, and 341.1 nm, the blends fractured in the brittle mode when the concentration of AIM was lower than 10 phr, whereas the blends showed ductile fracture when the AIM concentration reached 10 phr. It was concluded that the brittle-ductile transition of the PVC/AIM blends was independent of the particle size in the range of 55.2-341.1 nm. When the particle size was greater than 341.1 nm, however, the brittle-ductile transition shifted to a higher AIM concentration with an increase in the particle size. Furthermore, the critical interparticle distance was found not to be the criterion of the brittle-ductile transition for the PVC/AIM blends.

Reactive blending of modified polypropylene and polyamide 12: Effects of compatibilizer content on crystallization and blend morphology

The crystallization behavior and morphology of nonreactive and reactive melt-mixed blends of polypropylene (PP) and polyamide (PA12; as the dispersed phase) were investigated. It Was found that the crystallization behavior and the size of the PA12 particles were dependent on the content of the compatibilizer (maleic anhydride-modified polypropylene) because an in situ reaction occurred between the maleic anhydride groups of the compatibilizer and the amide end groups of PA12. When the amount of compatibilizer was more than 4%, the PA12 did not crystallize at temperatures typical for bulk crystallization. These finely dispersed PA12 particles crystallized co-incidently with the 1313 phase. The changes in domain size with compatibilizer content were consistent with Wu's theory. These investigations showed that crystallization of the dispersed phase Could not be explained solely by the size of the dispersion. The interfacial tension between the polymeric components in the blends may yield information on the fractionation of crystallization.

Abnormal pressure dependence of the phase boundaries in TL/PEO/P(EO-b-DMS) ternary mixtures

The cloud-point temperatures (T-cl's) of both binary poly(ethylene oxide) (PEO)-poly(ethylene oxide-b-dimethylsiloxane) [P(EO-b-DMS)] and ternary[toluene/PEO/P(EO-b-DMS)] systems were determined by light scattering measurements at atmospheric pressure. The phase separation behavior upon cooling in the ternary system has been investigated at atmospheric pressure and under high pressure and compared to the phase behavior in the binary system. The phase transition temperatures have been obtained for all of the samples. As a result, the pressure induces compatibility in the binary mixtures, but for the ternary system, pressure not only can induce mixing but also can induce phase separation.

Thermodynamics of phase behavior in PEO/P(EO-b-DMS) homopolymer and block co-oligomer mixtures under pressure

The cloud-point temperatures (T-cl's) of poly(ethylene oxide) (PEO) and poly(ethylene oxide)-block-polydimethylsiloxane (P(EO-b-DMS)) homopolymer and block-oligomer mixtures were determined by turbidity measurements over a range of temperatures (105 to 130degrees), pressures (1 to 800 bar), and compositions (10-40 wt.-% PEO). The system phase separates upon cooling and T-cl was found to decrease with an increase in pressure for a constant composition. In the absence of special effects, this finding indicates negative excess volumes. Special attention was paid to the demixing temperatures as a function of the pressure for the different polymer mixtures and the plots in the T-phi plane (where phi signifies volume fractions). The cloud-point curves of the polymer mixture under pressures were observed for different compositions. The Sanchez-Lacombe (SL) lattice fluid theory was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalphy of mixing, and the volume changes of mixing. The calculated results show that modified P(EO-b-DMS) scaling parameters with the new combining rules can describe the thermodynamics of the PEO/P(EO-b-DMS) system well with the SL theory.

Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Functionalization of an ethylene-propylene copolymer with allyl (3-isocyanate-4-tolyl) carbamate

An ethylene-propylene copolymer (EPM) was functionalized with an iso cyanate-bearing unsaturated monomer, allyl(3-isocyanate-4-tolyl) carbamate (TAI), with dicumyl peroxide as an initiator in a xylene solution. Fourier transform infrared (FTIR) was used to confirm the formation of EPM-g-TAI. The peak at 2273 cm(-1), characteristic of -NCO groups in EPM-g-TAI, revealed evidence of grafting. The grafting degree was determined with both chemical titration and FTIR. The grafting degree could be adjusted, and the maximum was over 6 wt % without any gelation. The molar mass distribution of EPM-g-TAI was narrower than that of EPM. The rheological behavior of both EPM-g-TAI and EPM was investigated with a rotational rheometer. The apparent viscosity of EPM-g-TAI was higher than that of EPM and increased with an increasing grafting degree of TAI. Surface analysis by contact-angle measurements showed that contact angles of EPM-g-TAI samples to a given polar liquid decreased with an increasing grafting degree of TAI. We also obtained the dispersion component of the surface free energy (gamma(S)(d)), the polar component of the surface free energy (gamma(S)(d)), and the total surface free energy (gamma(S) = gamma(S)(d) + gamma(S)(p)) of the grafted EPM. These parameters increased with the enhancement of the grafting degree, which gave us a quantitative estimation of the polar contribution of the grafted TAI to the total surface free energy of EPM-g-TAI.

Conductive hybrids from water-borne conductive polyaniline and (3-glycidoxypropyl)trimethoxysilane

Free-standing conductive films of organic-inorganic hybrids were prepared employing the sol-gel process of (3-glycidoxypropyl)trimethoxysilane (GPTMS) and water-borne conductive polyaniline (cPANI) in water/ethanol solution. The hybrids displayed a percolation threshold for electrical conductivity at a volume fraction of 2.1% polyaniline (PANI); the maximum conductivity of the hybrids reached 0.6 S/cm. GPTMS showed good compatibility with water-borne cPANI during the sol-gel process, and freestanding conductive films were obtained at room temperature. Transmission electron microscopy images of the hybrids indicated that the cPANI was dispersed in the inorganic phase in nanoscale. Because of good confinement of cPANI chains in the inorganic network, water resistance of the hybrid films was significantly improved compared with that of pure cPANI; the electrical conductivity of the films kept stable for 6-7 days soaking in water, whereas it decreased sharply for 1 day soaking for the pure cPANI.