Crystallinity Of Blends Research Articles

Study on electron‐beam‐irradiated (linear low‐density polyethylene)/(soya powder) blends under outdoor exposure

AbstractLinear low‐density polyethylene was blended with soya powder, and the blends were compatibilized with epoxidized natural rubber having 50 mol% of epoxidation. The content of soya powder was varied from 0 to 40 wt%. The blends were irradiated at 30 kGy with an electron beam. Degradation of the irradiated blends was evaluated by exposing the samples to an outdoor environment according to ISO 877.2. The degradation was monitored by changes in the tensile, morphological, and thermal properties, as well as the molecular structure and weight loss. The tensile strength and elongation at break (Eb) of the exposed samples decreased as a function of exposure period. The irradiated blends exhibited higher retention of tensile strength and Eb than nonirradiated blends after 1 year of exposure. The crystallinity of the irradiated blends increased upon exposure, though the nonirradiated blends showed higher crystallinity indicating higher degradability. Weight loss of the irradiated blends showed less change after 6 months of outdoor exposure, but significant change was observed after 1‐year exposure. The molecular weight changes of the irradiated blends exhibited the same trend as weight loss. All the results confirmed that the degradability of the irradiated blends was comparable to that of the nonirradiated blends upon long‐term outdoor exposure. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers

Fractional Crystallization and Phase Segregation in Binary Miscible Poly(butylene succinate)/Poly(ethylene oxide) Crystalline Blends: Effect of Crystallization Temperature

AbstractThe effects of crystallization temperature of PBS (TIC,PBS) on the fractional crystallization, phase segregation, and crystalline morphology of PEO in their miscible crystalline/crystalline blends are investigated. The crystallization kinetics and phase segregation of PEO are considerably influenced by TIC,PBS. A higher TIC,PBS results in the crystallization of PEO at an extremely large degree of supercooling and may facilitate the segregation of PEO within the interlamellar regions of PBS. At a high TIC,PBS (e.g., 95 °C), the long period, thickness of amorphous and crystalline layers of PBS increase upon blending with PEO. The TIC,PBS dependence of phase segregation of the PEO component is discussed from a thermodynamic as well as a kinetic perspective.magnified image

Solubilization of Genistein in Poly(oxyethylene) through Eutectic Crystal Melting

Solid-liquid phase diagrams of binary crystalline blends of genistein with poly(ethylene oxide) (PEO) and poly(ethylene glycol) (PEG) were established experimentally and theoretically based on the combined Flory-Huggins free energy of liquid-liquid phase separation and the phase field free energy pertaining to crystal solidification. The liquidus lines obtained self-consistently were found to agree well with trends of depressed crystal melting transitions in genistein/PEO and genistein/PEG blends, exhibiting eutectic phase behavior. Of particular importance is the lowering of the eutectic temperature of the genistein/PEO blend by about 60 °C upon switching to the genistein/PEG system. The occurrence of interspecies hydrogen bonding between genistein molecules and both PEO and PEG chains, albeit weak, was noticed by Fourier transform infrared spectroscopy. The improved solubility of genistein in PEG can be attributed not only to lowering of the molecular weight of PEG utilized, but also to its terminal hydroxyl groups. This eutectic melting approach by PEG solvent is sufficiently effective in solubilizing genistein crystals that development of genistein-containing drugs might be feasible for injection and/or oral administration.

Preparation and study of a thermo-responsive membrane using binary liquid crystal mixtures of cholesteryl cetyl ether and cholesteryl oleyl carbonate

A facile method for the synthesis of thermotropic liquid crystalline cholesteryl cetyl ether (CCE) was carried out from cholesterol and cetyl alcohol using montmorillonite K-10 as an acid catalyst. The aim of this study was to investigate the use of liquid crystalline blends of CCE and cholesteryl oleyl carbonate (COC) with appropriate crystal to smectic phase temperature (Tc–s) just above body temperature as a temperature-modulated drug permeation system. Using 30/70 mol ratio of COC/CCE, a mixture of desirable phase transition temperature was obtained. The phase transition behavior of COC/CCE binary liquid crystalline mixture was established by differential scanning calorimetry and polarizing optical microsopy. The COC/CCE-embedded cellulose nitrate membrane was used by an in vitro drug penetration studies. Paracetamol and mesalazine were chosen as hydrophobic and hydrophilic drug models, respectively. Paracetamol permeability through the membrane was higher at temperatures above the phase transition of liquid crystal (LC) blends (39 °C) than its permeability below the phase transition temperature of liquid crystal blends (30 °C). The drug penetration through LC-embedded cellulose membrane was influenced by the pore size of the membrane and therefore the adsorbed amount of LC. There was no penetration of mesalazine through that membrane presumably, due to the differences in hydrophilicity of LC-embedded membrane and permeated drug.

Processing and Characterization of High Density Polyethylene/Ethylene Vinyl Acetate Blends with Different VA Contents

Different series of high density Polyethylene/Ethylene Vinyl Acetate (HDPE/EVA) blends were prepared via melt blending in a corotating intermeshing twin screw extruder. The effects of VA percentage and EVA loading ratio on the thermal, rheological viscoelastic, mechanical, and fracture toughness of the blends were analyzed. The results showed that the addition of EVA to HDPE reduces the thermal, elastic, and viscoelastic properties of the blends. The microscopic examination of the fracture surface confirmed the ductile fracture of HDPE/EVA blends for all blend ratios and VA percentages. Increasing the EVA ratio and VA content caused a significant reduction in the blend crystallinity but had no significant effect on melting temperature. The complex viscosity increased with increasing the percentage of EVA due to the restriction of molecular mobility and reduction of free volume, induced by the addition of EVA. The storage modulus decreased with increasing the EVA ratio and temperature, while it increased with increasing the frequency. Young’s modulus, yield strength, and fracture strain decreased with increasing the EVA ratio. Similarly, the fracture toughness decreased proportional to the EVA percentage. Finally the results indicated that the VA content has significant effects on the mechanical, thermal, and dynamic properties of HDPE/EVA blends.

Preparation of poly(ε‐caprolactone)/poly(ε‐caprolactone‐co‐lactide) (PCL/PLCL) blend filament by melt spinning

AbstractPoly(ε‐caprolactone)/poly(ε‐caprolactone‐co‐lactide) (PCL/PLCL) blend filaments with various ratios of PCL and PLCL were prepared by melt spinning. The effect of PLCL content on the physical properties of the blended filament was investigated. The melt spinning of the blend was carried out and the as spun filament was subsequently subjected to drawing and heat setting process. The addition of PLCL caused significant changes in the mechanical properties of the filaments. Crystallinity of blend decreased with the addition of PLCL as observed by X‐ray diffraction (XRD) and differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) revealed that the fracture surface becomes rougher at higher PLCL content. It may be proposed that PCL and PLCL show limited interaction within the blend matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Changes in the crystallinity and mechanical properties of poly(l-lactic acid)/poly(butylene succinate-co-l-lactate) blend with annealing process

Biodegradable polymer blends of poly(l-lactic acid) (PLLA) and poly(butylene succinate-co-l-lactate) (PBSL) at various blending ratios are prepared. The blending of PLLA with PBSL results in an increase in the ductility and thermal stability of the blend. However, flexural strength and modulus, as well as loss modulus, decrease with an increase in PBSL content. Annealing is employed to increase blend crystallinity and subsequently improve the mechanical properties of the PLLA/PBSL blend. The influences of annealing time on the crystal modification, thermal properties, and mechanical properties of the PLLA/PBSL blend are investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and three-point bending test, respectively. Crystalline peaks are found in the XRD patterns of all annealed samples. DSC analysis reveals that the degree of crystallinity is enhanced with an increase in annealing time. The flexural modulus also increases with annealing time due to the change in crystalline phases. However, longer periods of annealing, especially over 20 h, result in thermal degradation and subsequently reduce the modulus value of the PLLA/PBSL blend.

Dynamic mechanical, thermal, physico-mechanical and morphological properties of LLDPE/EMA blends

The effect of blend composition on the morphology, dynamic mechanical properties, thermal and physico-mechanical properties of linear low density polyethylene (LLDPE)/ ethylene-co-methyl acrylate (EMA) blends were studied. The blend showed both dispersed and continuous phase morphology that depends on the blend composition. A co-continuous structure is formed for blends containing 50 wt% of EMA. Dynamic mechanical studies showed that flexibility of the blend enhanced with the expansion of the amorphous region as EMA content increased. However, two separate melting temperature peak observed in differential scanning calorimetry (DSC) analysis indicate that the blends are immiscible in crystalline region of the two polymers. X-ray diffraction (XRD) studies showed that crystallinity of blends decreases with increase in EMA content and negative deviation of tensile strength from the mixing rule indicates the poor interfacial adhesion between the two components. FTIR spectroscopy established the lack of chemical interaction between LLDPE and EMA, which support the SEM, DSC, DMA and XRD observations. Parallel-Voids model has been applied to characterize phase morphology of these blends.

Mechanical properties of poly(ether ether ketone)/poly(ether ketone) blends: Use of simple models relating normalized tensile parameters

AbstractIn this study, mechanical properties such as tensile properties, flexural properties, and Izod impact strength of poly(ether ether ketone) (PEEK) and poly(ether ketone) (PEK) blends at PEK concentration from 0 to 0.42 volume fraction were studied. The blends of PEEK and PEK of different compositions were prepared by extrusion in a single‐screw extruder. With increase in the PEK concentrations, the tensile strength, flexural strength, and modulus increased whereas the tensile modulus and the impact strength decreased. Homogeneous dispersion and adhesion of PEK in PEEK was shown by the morphological studies. Crystallinity of blends influenced the tensile modulus and the impact strength. Using simple models to relate normalized tensile parameters where the data were divided by the crystallinity of the blends and of the PEEK matrix, respectively, supported the experimental results. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

The crystallinity and miscibility of syndiotactic polystyrene blends after mixing with low molar mass liquid crystal or commercial lubricant

The quantities of the crystallinity of syndiotactic polystyrene (SPS) blended with another polymer in the group of poly(α-methyl styrene), poly(n-butyl methacrylate) or poly(cyclohexyl acrylate) with or without the additives were measured by X-ray diffraction and calculated by Ruland’s method. The SPS was synthesized by using metallocene catalyst and modified-methylaluminoxane as cocatalyst. The additive of low molar mass liquid crystal chemical (cyclohexyl-biphenyl-cyclohexane (CBC33)) or lubricant (glycerol monostearate (GMS)) was individually added to the blends of SPS in order to investigate the effects on the crystallinity of the blended SPS. From the experimental results, it was found that the percent crystallinities of the blends decreased with decreasing the percent of SPS in the blend because of the dilution of SPS. The depression of the percent crystallinity was in the order of PaMS > PCHA > PBMA according to the compatibility with SPS. The addition of GMS or CBC33 slightly decreased the percent crystallinity of the pure SPS. The addition of GMS impeded the depression of the SPS crystallinity in the blends, because their percent depression from pure SPS is similar (at around 25%) regardless to the components of the blends. The blends with added CBC33 have the similar depression of crystallinity as the pure blends because of the low concentration of CBC33 and the good compatibility of CBC33 with the SPS.

Microstructure and Dynamics of Semicrystalline Poly(ethylene oxide)−Poly(vinyl acetate) Blends

The microstructure and dynamics of semicrystalline, melt-miscible poly(ethylene oxide)/poly(vinyl acetate) (PEO/PVAc) blends were investigated using small-angle X-ray scattering (SAXS) and broadband dielectric relaxation spectroscopy, respectively. PEO/PVAc blends with selected compositions were crystallized, and SAXS was used to determine the location of the noncrystallizable PVAc in the structure. Values of the microstructural parameters indicate that little, if any, PVAc is incorporated into interlamellar regions under these crystallization conditions, but PVAc diffuses to interfibrillar regions during the crystallization process. For crystalline blends, a dielectric relaxation appears in the same location as the neat PEO α-process, indicating the presence of relatively mobile amorphous segments consisting almost entirely of PEO, in blends with compositions having as much as 50% PVAc. Considering the findings from the SAXS experiments, we attribute αPEO in the blends to the segmental process of the mob...

Highly transparent thermoplastic elastomer from isotactic polypropylene and styrene/ethylene‐butylene/styrene triblock copolymer: Structure‐property correlations

AbstractPolypropylene (PP) is one of the most useful general purpose plastics. However, the poor transparency and brittleness of PP restricts its applications in the field of medical and personal care where silicone and polyvinyl chloride (PVC) are presently used. This work concentrates on developing highly transparent elastomeric PP blends and also thermoplastic elastomer by blending isotactic polypropylene (I‐PP) with styrene/ethylene‐butylene/styrene (SEBS) triblock copolymer. PP/SEBS blend derived from high melt flow index (MFI) PP and high MFI SEBS exhibit remarkable transparency (haze value as low as 6%) along with good percentage of elongation and processability. The reduction in difference of refractive index (RI) between PP and SEBS has been observed by blending SEBS with PP. The wide angle X‐ray diffraction studies show that there is significant reduction in the percentage crystallinity of PP by the addition of SEBS block copolymer. Temperature‐dependent polarized light microscopy studies reveal the reduction in spherulites size by the addition of SEBS block copolymer. Transmission electron micrographs show that the SEBS polymer forms a fine lamellar structure throughout the PP matrix with phase inversion at higher SEBS concentration. Development of phase morphology, crystalline morphology, and crystallinity in different blends has been analyzed and microstructure‐haze correlations have been developed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers

Influence of static and dynamic crosslinking techniques on the transport properties of ethylene propylene diene monomer rubber/poly (ethylene-co-vinyl acetate) blends

The transport characteristics of dynamically and statically cross-linked Ethylene Propylene Diene Monomer/poly (ethylene-co-vinyl acetate) (EPDM/EVA) blends have been examined in the temperature interval of 28–58 °C using benzene, toluene and xylene as probe molecules. The dynamically vulcanized blends exhibited enhanced properties on the sorption and diffusion features compared to the corresponding statically vulcanized blends. In both the cases, as the EVA content increased in the blends, the solvent uptake decreased. The experimental observations have been correlated with the phase morphology of the blends, using scanning electron micrographs. The crystallinity of the blends was studied using X-ray diffraction patterns. Among the three vulcanising systems, viz, sulphur, dicumyl peroxide (DCP), and a mixture consisting of sulphur and peroxide, employed for the matrix, the DCP cross linked system exhibited the lowest solvent uptake. The molar mass between cross links and the diffusion coefficients have been computed to complement the observed sorption behaviour.

Melt-crystallization behavior and isothermal crystallization kinetics of crystalline/crystalline blends of poly(ethylene terephthalate)/poly(trimethylene terephthalate)

The melt-crystallization and isothermal melt-crystallization kinetics of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends (PET/PTT) were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. Although PET and PTT in the binary blends are miscible at amorphous state, they will crystallize individually when cooled from the melt. In the DSC measurements, PET component with higher supercooling degree will crystallize first, and then the crystallite of PET will be the nucleating agent for PTT, which induce the crystallization of PTT at higher temperature. On the other hand, in both blends of PET80/PTT20 and PET60/PTT40, the PET component will crystallize at higher temperature with faster crystallization rate due to the dilute effect of PTT. So the commingled minor addition of one component to another helps to improve the crystallization of the blends. For blends of PET20/PTT80 and PET40/PTT60, isothermal crystallization kinetics evaluated in terms of the Avrami equation suggest different crystallization mechanisms occurred. The more PET content in blends, the fast crystallization rate is. The Avrami exponent, n = 3, suggests a three-dimensional growth of the crystals in both blends, which is further demonstrated by the spherulites formed in all blends. The crystalline blends show multiple-melting peaks during heating process.

Theory and computation of photopolymerization-induced phase transition and morphology development in blends of crystalline polymer and photoreactive monomer

A hypothetical phase diagram of a crystalline polymer/photoreactive monomer mixture has been calculated on the basis of phase field (PF) free energy of crystal solidification in conjunction with Flory-Huggins (FH) free energy of liquid-liquid demixing to guide the morphology development during photopolymerization of poly(ethylene oxide)/triacrylate blend. The self-consistent solution of the combined PF-FH theory exhibits a crystalline-amorphous phase diagram showing the coexistence of solid+liquid gap bound by the liquidus and solidus lines, followed by an upper critical solution temperature at a lower temperature. When photopolymerization was triggered in the isotropic region, i.e., slightly above the crystal melting transition temperatures, the depressed melting transition line moves upward. When it surpasses the reaction temperature, both crystallization and phase separation occur. The temporal evolution of phase morphology is examined in the context of time-dependent Ginzburg-Landau equations coupled with the energy balance (heat conduction) equation using the aforementioned PF-FH free-energy densities. Of particular interest is that the emerged morphology in the crystalline blends depends on the competition between dynamics of liquid-liquid phase separation and/or liquid-solid phase transition (i.e., crystallization) and photopolymerization rates.

Evaluation of photodegradation in LDPE/modified starch blends

Photodegradation of LDPE/modified starch blends 80/20 m/m has been examined by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X ray diffraction (DRX) before and after exposure to ultraviolet radiation (UV). Samples were exposed to UV in the laboratory for periods of 6, 24, 48 and 60 hours. The main alteration in the polymeric material after exposure to the radiation was a decrease in the mechanical properties, tensile strength and elongation. There were also changes in the chemical structure of the blend with an increase in the carbonyl and vinyl indices, 65.58 and 53.29%, respectively. The analysis of the blend crystallinity pointed to the formation of a new crystalline symmetry that did not exist before the irradiation.

The effect of ionic interaction on the miscibility and crystallization behaviors of poly(ethylene glycol)/poly(L‐lactic acid) blends

AbstractThe effect of end groups (2NH2) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly(L‐lactic acid) (PLLA) were investigated. The results of conductivity meter and dielectric analyzer (DEA) implied the existence of ions, which could be explained by the amine groups of PEG gaining the protons from the carboxylic acid groups of PLLA. The miscibility of PEG(2NH2)/PLLA blends was the best because of the ionic interaction as compared with PEG(2OH, 1OH‐1CH3, and 2CH3)/PLLA blends. Since the ionic interaction formed only at the chain ends of PEG(2NH2) and PLLA, unlike hydrogen bonds forming at various sites along the chains in the other PEG/PLLA blend systems, the folding of PLLA blended with PEG(2NH2) was affected in a different manner. Thus the fold surface free energy played an important role on the crystallization rate of PLLA for the PEG(2NH2)/PLLA blend system. PLLA had the least fold surface free energy and the fast crystallization rate in the PEG(2NH2)/PLLA blend system, among all the PEG/PLLA systems studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Dynamics in complex systems: Dendrimer–polymer blends in electric and mechanical fields

An investigation was carried out on the molecular dynamics of blends composed of poly(amidoamine) (PAMAM) dendrimers with ethylenediamine core and amino surface groups (generations 0 and 3) and three linear polymers: poly(propylene oxide) – PPO and two block copolymers, poly(propylene oxide)/poly(ethylene oxide) – PPO/PEO with different mole ratios: 29/6 (amorphous) and 10/31 (crystalline). The results were generated over a broad range of frequency and temperature by Dielectric Relaxation Spectroscopy (DRS) and Dynamic Mechanical Spectroscopy (DMS). Dielectric spectra of dendrimers in the PPO matrix reveal a decrease in the time scale of normal and segmental relaxation with increasing dendrimer concentration. In the amorphous blends with 29PPO/6PEO matrix, no effect of concentration on the time scale of normal and segmental processes was observed. But in the crystalline blends with 10PPO/31PEO matrix, relaxation time increases with increasing dendrimer concentration. Results acquired by DRS and DMS were contrasted and the obtained relaxation times were found to be in excellent agreement. A detailed analysis of the effect of generation and concentration of dendrimers, hydrophilicity and morphology of the polymer matrix and temperature on the molecular origin, the shape of the relaxation spectra, the dielectric relaxation strength and the frequency location for the maximum loss in dendrimer–polymer blends is provided.

Fuzzy set implementation for controlling and evaluation of factors affecting melting, crystallinity and interaction in polymer blends

In this study, the factors (i.e. weight fractions, crystallization temperatures and interaction such as hydrogen bonding) affecting melting, crystallinity, interaction parameters and miscibility of polymer blends (PB) have been studied by implementation of a fuzzy set. The interaction parameters were calculated using the Nishi-Wang equation, which is based on the Flory-Huggins theory. The values of interaction parameters χ 12 were negative for all blend compositions suggesting that χ 12 depends on the volume fraction ( Φ) of the polymer. The various characteristics for the case study was synthesized and converted into relative weights w.r.t fuzzy set method. The fuzzy set analysis for the case study reveal increase as confirmed by the experimental data. The application of the fuzzy set methodology offers reasonable prediction and assessment for detecting yield in polymer blends.

Miscibility and melting properties of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting properties of binary crystalline blends of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) (PEN/PTT) have been investigated with differential scanning calorimetry (DSC). The glass transition and cold crystallization behaviors indicated that in PEN/PTT blends, there are two different amorphous phases and the PEN/PTT blends are immiscible in the amorphous state. The polymer–polymer interaction parameter, \( \chi _{12}\), calculated from equilibrium melting temperature depression of the PEN component was −1.791 × 10−5 (300 °C), revealing miscibility of PEN/PTT blends in the melt state.