Transport properties of water in hydroxypropyl methylcellulose

The relation between the self-diffusion coefficient, D_self, of water and the free volume hole size, V_h, has been investigated in a hydroxypropyl methylcellulose (HPMC)-water system in the water content range 0.08-0.36 w/w, at room temperature. Furthermore, the thermal properties of the water in the HPMC-water system, as measured with differential scanning calorimetry (DSC) and the tensile storage, E′, and tensile loss, E″, moduli, of the HPMC-water systems, as determined with dynamic mechanical analysis (DMA), have been probed. Pulsed-field gradient nuclear magnetic resonance (PFG NMR) was used to measure the D_self of water and positron annihilation lifetime spectroscopy (PALS) was used to measure the ortho-Positronium (o-Ps) lifetime in the HPMC-water system. The glass transition temperature of the HPMC was found to be reduced by the water to room temperature in the water content range 0.10-0.15 w/w. The relation between ln D_self of water and the inverse free volume hole size of the HPMC-water system was non-linear. Furthermore, the PALS measurements showed that molecular water co-existed with water clusters in the HPMC-water system.     

Surface characterizations of spin-coated films of ethylcellulose and hydroxypropyl methylcellulose blends

Films of pure ethylcellulose (EC) and hydroxypropyl methylcellulose (HPMC) polymers and EC/HPMC blends were prepared from solutions by spin coating where isopropyl alcohol (IPA), water, and IPA/water cosolvent were used as solvents. Surface structures of the films were investigated using optical microscopy, atomic force microscopy (AFM), and Raman mapping and spectroscopy. For the films prepared from EC/HPMC blend solutions using the IPA/water cosolvent, different domain structures such as islands or pits and phase separation between EC and HPMC were observed by optical microscopy and AFM. The nature of the polymer components on the surface of the films was identified by Raman mapping and spectroscopy. Experimental results also indicated that polymer composition, solvent, and temperature during spin coating had significant impacts on surface structures of the films.     

Rheological properties of UHMWPE/iPP blends

The effects of isotactic polypropylene (PP) on the rheological properties of ultra high molecular weight polyethylene (UHMWPE) have been measured in a broad range of composition (0, 5, 15, 30 wt% PP) at various temperatures (110, 130, and 150°C) and a specific gel concentration of 6 wt%. The result showed that the viscosity of the UHMWPE significantly decreased with the addition and increasing amount of PP. Regardless of temperature, the viscosity function followed the power‐law behavior. Copyright © 2009 John Wiley & Sons, Ltd.     

Rheological properties of asphalt/SBS/clay blends

The effect of the addition of clay as a third component in polymer modified asphalts has been investigated. After a preliminary investigation on the binary asphalt/clay and polymer/clay blends, the tertiary blends were prepared by adding the clay and polymer to the asphalt, either separately or in the form of a premixed master batch. Intercalated nanocomposites with comparable interlayer distances and glass transition temperatures were obtained in both cases. However, the results show that the mixing procedure significantly affected the final rheological properties. The master curves built in the linear viscoelastic range and represented in both the frequency and the temperature domains help to visualize and evaluate such differences.     

Electrospinning of hydroxypropyl methylcellulose trimellitate solutions

Nonwoven fiber mats of hydroxypropyl methylcellulose trimellitate(HPMCT) with potential applications in controlled delivery of drugs and scaffolds for tissue cultures have been successfully fabricated by electrospinning of HPMCT solutions.The formation and diameters of HPMCT fibers fabricated by electrospinning were strongly influenced by the solvents employed,electrostatic field strength,and solution concentrations.The electrospun products generated from all HPMCT solutions with various weight-average mole...     

Interactions and partitioning of diluents/plasticizers in hydroxypropyl methylcellulose and polyvinyl alcohol homopolymers and blends. Part II: Glycerol

The interactions and partitioning of glycerol in polyvinyl alcohol (PVA), hydroxypropyl methylcellulose (HPMC) and their blends has been studied by means of torsional braid analysis (TBA). Glycerol was shown to be a more efficient plasticizer for PVA than HPMC in agreement with solubility parameter prediction. Kelley-Bueche-type equations were fitted to the experimentalTg data and initial slopes yielded an interaction parameter,Kø, between glycerol and the two polymers. Incorporation of glycerol in PVA/HPMC blends did not alter the incompatibility of the two polymers and plasticized both phases. The compositions of the two plasticized phases were calculated from Kelley-Bueche expressions fitted to the experimental data, enabling determination of the glycerol partition coefficients into the two phases. In blends with 20–60% PVA, glycerol partitioned selectively into the PVA-rich phase whereas in the system with 80% PVA, glycerol partitioned selectively into the HPMC-rich inclusions.     

Morphologies and properties of plasticized starch/polyamide compatibilized blends

A new sodium carboxymethylcellulose (CMC) compatibilized glycerol-plasticized starch/polyamide PA11 blend having improved mechanical properties was realized in a one step extrusion process. Blends were prepared in internal mixer and twin screw extruder. Mechanical properties (stress and strain at break) are improved by adding 1 wt% of CMC. Rheological characterization and scanning electron microscopy show that a co-continuous morphology is observed on a wide range of TPS amount.     

Interactions and partitioning of diluents/plasticizers in hydroxypropyl methylcellulose and polyvinyl alcohol homopolymers and blends. Part I: Diethylene glycol

The interactions and partitioning of diethylene glycol (DEG) in polyvinyl alcohol (PVA), hydroxypropyl methylcellulose (HPMC) and their blends has been studied. DEG acted as efficient plasticizer for both homopolymers, lowering theirT _g and relative rigidity. Kelly-Bueche-type equations were fitted successfully to the experimental data and yielded an interaction parameter,K , between DEG and each polymer. Incorporation of DEG into two-phase blends of PVA and HPMC with 40, 50 and 60% PVA did not change the significant incompatibility of the two components and plasticized both phases. Composition calculations based on Kelley-Bueche-type expressions fitted to the experimental data afforded determination of the partition coefficients of DEG into the two phases of the blends. In the case of the 5050 weight% system, it partitioned almost equally into both phases. The results are discussed in terms of the DEG affinity to interact with the two polymers by means of the dispersive, polar and hydrogen-bonding contribution to the solubility parameters.     

Thermal extrusion of cellulose using hydroxypropyl methylcellulose

Cellulose - Hydroxypropyl methylcellulose (HPMC), a cellulose derivative, is highly water soluble, viscoelastic, and thermoplastic. However, the thermoplasticity of HPMC has not yet been studied in...     

Interactions and partitioning of diluents/plasticizers in hydroxypropyl methylcellulose and polyvinyl alcohol homopolymers and blends. Part III: Polyethylene glycol 400

The interactions and partitioning of polyethylene glycol 400 (PEG400) in hydroxypropyl methylcellulose (HPMC), polyvinyl alcohol (PVA) and their blends have been investigated by means of torsional braid analysis (TBA). PEG400 was shown to be a better plasticizer for HPMC than PVA, in agreement with solubility parameter predictions. Incorporation of PEG400 in blends of PVA and HPMC did not alter the incompatibility between the two homopolymers and plasticized both phases. The PEG400 content in the two phases was calculated by fitting Kelley-Bueche and quadratic expressions to the experimental data, enabling determination of the PEG400 partition coefficient. The data showed a selective partitioning of PEG400 in the HPMC phase for plasticizer contents less than 20% w/w. At higher concentrations, PEG400 continued to partition selectively into the HPMC phase for blends with 60 and 80% PVA but started partitioning in the PVA phase for blends with 20 and 40% PVA.     

Processing window for extrusion foaming of hydroxypropyl methylcellulose

Foamed materials are gaining an increased interest due to their good mechanical properties in relation to their low densities and an increased industrial demand can be expected. A few less attractive issues can however be associated with commodity foamed products. For instance the raw-material often originates from non-renewable, fossil-based, sources. Furthermore, degradation in nature is slow, therefor the disposed product is burned or end up in landfills. One possibility to reduce the impact on nature could be to produce foams from natural polymers such as starch or cellulose. In this study the possibility to produce foams from hydroxypropyl methylcellulose (HPMC) with water as blowing agent, by continuous extrusion, was investigated. A pre-study using a capillary viscometer, batch-extruder, was conducted to evaluate the foamability of HPMC. Due to promising results further experiments were conducted with a single-screw extruder. The goal was to find an adequate processing window for foaming. It was concluded that HPMC could successfully be foamed by continuous extrusion, although a careful tailoring of the processing parameters was required. Crucial parameters were here the temperature, pressure and residence time distribution in the extruder. Regions of the extruded foams were examined using optical and scanning electron microscopy and HPMC foams with a density in the range of that of fossil-based polymeric foams could be produced.     

Combined effect of hydroxypropyl methylcellulose and hydroxypropyl-β-cyclodextrin on physicochemical and dissolution properties of celecoxib

Investigation on the influence of hydroxypropyl methylcellulose (HPMC) on solubility and dissolution properties of celecoxib/hydroxypropyl-β-cyclodextrin system was carried out, with the ultimate goal of enhancing the drug bioavailability. ¹H-NMR and ¹³C-NMR spectroscopy were first performed to elucidate the type of interactions between celecoxib (CEL) and hydroxypropyl-β-cyclodextrin (HP-β-CD). Then, solubility studies in the absence and in the presence of HPMC were carried out in aqueous solution. After heating in autoclave of CEL/HP-β-CD/HPMC suspensions a synergistic increasing effect on the aqueous solubility of CEL was observed. In fact, the presence of both HP-β-CD (0.05 M) and HPMC (0.25% w/v) gave rise to a 330-fold CEL solubility increase, whereas the cyclodextrin alone provided a 34-fold increase. Gibbs free energy values calculated from phase solubility data were all negative, indicating the spontaneous nature of CEL solubilization, and they decreased in the presence of HPMC, demonstrating that the solubilization conditions became more favorable. CEL/HP-β-CD and CEL/HP-β-CD/HPMC solid systems (physical mixtures and coevaporated products) were characterized by differential scanning calorimetry and infrared spectroscopy. Results suggested that the coevaporation method yields a high degree of amorphous entities and indicated the formation of a CEL/HP-β-CD complex in the coevaporated products. The positive effect of HPMC is particularly evident when looking at the CEL dissolution rate from the binary and ternary solid systems. Specifically, the percent of CEL dissolved after 10 min. resulted 84.21% for ternary coevaporated product and 50.18% for binary coevaporated product with respect to 13.10% for the drug alone.     

Determination of methylcellulose and hydroxypropyl methylcellulose food gums in food and food products: collaborative study

A collaborative study was performed to determine the reproducibility of a method for the determination of methylcellulose (MC) and hydroxypropyl methylcellulose (HPMC) in food. These widely used food gums possess unusual solubility characteristics and cannot accurately be determined by existing dietary fiber methods. The new method uses the enzyme-digestion procedure of AOAC Official Method 991.43. Digestate solutions must be refrigerated to fully hydrate MC or HPMC. The chilled solutions are filtered and analyzed by size-exclusion liquid chromatography. Collaborating laboratories received 28 samples containing MC or HPMC in the range of 0-100%. The sample set included blind duplicates of 5 food matrixes (bread, milk, fish, potato, and powdered juice drink). Cochran and Grubbs tests were used to eliminate outliers. For food samples containing MC, values for within-laboratory precision, repeatability relative standard deviation (RSDr), ranged from 4.2 to 16%, and values for among-laboratories precision, reproducibility relative standard deviation (RSDR), ranged from 11 to 20%. For HPMC samples, RSDr values ranged from 6.4 to 27%, and RSDR values ranged from 17 to 39%. Recoveries of MC and HPMC from the food matrixes ranged from 78 to 101%. These results show acceptable precision and reproducibility for the determination of MC and HPMC, for which no Official AOAC Methods exist. It is recommended that this method be adopted as AOAC Official First Action.     

Correlation between mechanical adhesion and interfacial properties of starch/biodegradable polyester blends

Biopolymers are preferred ingredients for the manufacture of materials because they are based on abundantly available and renewable raw materials that have benign environmental problems associated with their production, fabrication, use, and disposal; however, the wide use of biopolymers in engineering applications has not been achieved, mainly because of the inferior quality of many biopolymer‐based products. To overcome this limitation, studies have been initiated on blends of biopolymers and biodegradable synthetic polymers. We used the contact angle of probe liquids to measure the surface energy of polystyrene, the biodegradable polyesters polycaprolactone, poly(hydroxybutyrate‐co‐hydroxyvalerate), polylactic acid, polybutylene adipate terephthalate, and adipic poly(hydroxy ester ether), and normal starch. The surface energies were used to estimate the starch/polymer interfacial energy and work of adhesion. The calculated starch/polyester work of adhesion showed mixed correlation with published starch/polyester mechanical properties, indicating that factors other than interfacial properties might be dominant in determining the mechanical properties of some starch/polyester blends. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 920–930, 2001     

Rheological properties and microstructures of Carbopol gel network system

Carbopol gel systems have been studied using steady, oscillatory rheology, and cryoscanning electron microscopy (cryo-SEM) analysis in order to elucidate the nature of the different microstructures of the gel in relation to polymer concentration as well as triethanolamine (TEA) content. The effect of changing the concentration of Carbopol (0.1–4 wt%) for 0, 1, and 10 wt% TEA has been investigated. Cryo-SEM revealed that honeycomb structures were observed in the gel system depending on the amount of TEA and Carbopol while the irregular fibrous three dimensional gel network systems were seen at the lower level of polymer content even in the high concentration of TEA. In addition to that, as the amount of polymer was increased, strings of fibrous network became thicker and of honeycomb-like structure. Shape of storage modulus-shear stress curve in the dynamical rheometric study was significantly changed as a result of variation in the microstructures while frequency sweep curve and yield values obtained from the model fitting in the steady rheological measurements couldn't reflect the structural difference of Carbopol gels. Two distinct relaxation phenomena were appeared with increase in polymer concentration as well as TEA concentration. Temperature dependence of the stress sweep experiment was measured and shown that the effect of temperature (1–80 °C) on the shape of the curve was the similar trend with that of TEA and polymer concentrations, although the temperature dependency on the increment was much weaker than TEA concentration.     

Rheological properties and phase behavior of a hydroxypropyl cellulose-poly(ethylene glycol) system

The relaxation and phase behavior of solutions of hydroxypropyl cellulose in poly(ethylene glycols) of various molecular masses has been studied by dynamic mechanical analysis. The dynamic mechanical data are compared with the results of microinterferometry and polarization-microscopy measurements. The combination of optical and mechanical characteristics makes it possible to construct generalized phase- relaxation diagrams for the binary systems under study. Solutions based on lowmolecular-mass poly(ethylene glycol) are characterized by LC equilibrium. With an increase in the molecular mass of poly(ethylene glycol) in a certain temperature-concentration region, amorphous phase separation takes place and the phase diagram is the superposition of LC and amorphous equilibria. The relaxation properties of the systems are sensitive to the phase state and its transformation.     

Processing and characterization of LDPE/starch/PCL blends

Low-density polyethylene/plasticized starch/polycaprolactone blends were processed by conventional extrusion, injection molding, and film blowing techniques. The glass transition temperatures of plasticized starch were determined using differential scanning calorimetry. The blends were characterized by mechanical property measurements and scanning electron microscopy. The blend properties were found to depend not only on composition but also on the generated morphology. In films the fine dispersion of polycaprolactone phase in the polyethylene/starch matrix resulted in mechanical property increase, while in injection specimens there was property decrease due to phase coalescence. It appears that the different conditions existing at the two different shaping processes i.e. film blowing and injection molding could account for the final obtained morphology.     

Effect of hydrophobic modification of hydroxypropyl methylcellulose on silicone oil emulsions

To study the effect of hydrophobic modification of the emulsifier on the relationship between emulsion stability and polymer emulsifier concentration, silicone oil emulsions were prepared using hydroxypropyl methylcellulose (original HPMC) and HPMC stearoxy ether (hydrophobic HPMC) at concentrations around their overlap concentrations. Both HPMC types completely emulsified the silicone oil. However, the volume fraction of silicone oil in the emulsion prepared using hydrophobic HPMC was less than that that by the original HPMC, and the average oil droplet size in the former emulsion was less than that in the latter emulsion. Increasing HPMC concentration led to increase in both the amount of adsorbed polymer emulsifier and the storage moduli in the linear region, irrespective of which HPMC was used. Stress-strain sweep curves obtained by a rheo-optical method showed that emulsions stabilized by the hydrophobic HPMC flowed slowly, even beyond the yield stress, whereas emulsions prepared using the original HPMC flowed quickly beyond the yield stress. The storage moduli of the emulsions prepared by the hydrophobic HPMC were larger than those prepared using the original HPMC.     

Rheological properties of ground tyre rubber based thermoplastic elastomeric blends

This work analyses the rheological behaviour of thermoplastic elastomeric blends (TPE) based on ground tyre rubber (GTR), more specifically the rheological behaviour of binary and ternary polypropylene (PP) based blends with different rubber materials: an ethylene propylene diene monomer (EPDM), an ethylene propylene rubber (EPR) and GTR. The study was developed under steady-shear rate conditions by capillary rheometry at three different temperatures. Time–Temperature Superposition Principle (TTSP) was applied to the viscosity curves using a temperature dependent shift factor, allowing the construction of master curves for the analysed blends. The Cross-WLF model was used to predict the rheological parameters, giving numerical results for viscosity similar to the experimental data. GTR increased the blends viscosity. EPR showed rheological behaviour similar to PP, and EPDM presented higher power law behaviour. Pseudoplastic behaviour was observed for all the analysed blends. Incorporation of GTR in TPE blends for injection moulding purposes was found to be a feasible strategy to upcycle this type of potentially wasted material.