Rheology of Lyocell Solutions from Different Cellulose Sources

Rheological measurements were used to characterize the behavior of lyocell solutions, i.e., cellulose dissolved in N-methymorpholine-N-oxide. Cellulose sources included dissolving pulp, kraft pulp, sugar cane fibers, and kenaf fibers. The dominance of viscous behavior, G values, over elastic behavior, G values, is affected by cellulose concentration and molecular weight. At lower concentrations and degrees of polymerization (DP), dissolving pulp solutions show viscous, inelastic behavior at low frequencies. At higher concentration and DP, dissolving pulp solutions are more elastic at higher frequencies. Solutions prepared with kenaf and sugar cane fibers show similar properties to those using pure dissolving pulp, and comparisons suggest the molecular weight and/or the presence of other substances such as lignin in the cellulose from these alternative sources affect the rheology.     

Lyotropic Liquid Crystal Phases in Cellulose Acetate Phthalate/Hydroxypropyl Cellulose Blends

Cellulose and some of its derivatives form liquid crystalline solutions in a variety of solvents. The present work investigates cellulose acetate phthalate/hydroxypropyl cellulose blends in N,N-dimethylacetamide, in function of concentration and composition, by rheology, considering dynamic viscometry and oscillatory shear tests. The effects of composition, concentration, shear rate, and oscillatory deformation on the rheological functions determines the orientation or mobility of the chain segments in the shear field. Atomic force microscopy and polarized light microscopy studies on corresponding films show that specific interactions, such as the hydrogen bonds between cellulose acetate phthalate and the liquid crystalline component—hydroxypropyl cellulose, stabilizes the morphology, leading to the emergence of different formations typical for lyotropic liquid crystal phases. These studies contribute to a better knowledge of the specific interactions that generate and modify the liquid crystalline properties of cellulose derivatives, required by the applications in electronic domains.     

Dynamic Mechanical Properties of Soy Protein Filled Elastomers

Dynamic mechanical properties including temperature effect, stress softening, and Payne effect are studied on the elastomer composites filled with soy protein or carbon black. The comparison of protein composite with well-known carbon black composites provides further insight into the protein composites. The elastomers filled with soy protein aggregates give substantial reinforcement effect when compared with the unfilled elastomers. Approximately 400 times increase in shear elastic modulus was observed when 40% by weight of protein is incorporated into the elastomers. The sample films were cast from the particle dispersion of soy protein isolate and carboxylated styrene–butadiene latex. At the higher temperatures, the shear elastic modulus of soy protein-filled composites does not decrease as much as that of the carbon black-filled composites. The behavior of elastic and loss modulus under the oscillatory strain of different magnitude is similar to that of carbon black reinforced styrene–butadiene rubber. However, carbon black composites show a better recovery behavior after eight cycles of dynamic strain. The reduction of shear elastic modulus with dynamic strain (Payne effect) was compared with Kraus model and the fitting parameter related to the aggregate structure of the soy protein. A reasonable agreement between the theoretical model and experiment was obtained, indicating the Payne effect of the protein-related network structure in the elastomers could also be described by the kinetic agglomeration de-agglomeration mechanism.     

Rheological Studies of Microfibrillar Cellulose Water Dispersions

The rheological behaviour of microfibrillar cellulose (MFC) water dispersions has been investigated. For the first time a detailed study of shear dependent viscosity at low and high shear rate is presented. A peculiar time dependent behaviour measured in the area between 0 and 1000 s⁻¹ was identified. The study shows a hysteresis loop in the shear rate–viscosity relationship at low shear rate. Additional time dependent shear rate measurements were performed, and a hypothesis for a mechanism of interaction and formation of a fibrils network was suggested. Higher temperature caused lower viscosity values, and this difference was increased at higher shear rate values. Oscillatory measurements showed how the closeness of the fibrils helps network creations. Data obtained from high shear measurements showed that 1% MFC water dispersions had a dilatant behaviour at ultra high shear rates with values increasing from 120 to 300 Pa s in the area between 180,000 and 330,000 s⁻¹ .     

Review of the kinetics of alkaline degradation of cellulose in view of its relevance for safety assessment of radioactive waste repositories

The degradation of cellulose (a substantial component of low- and intermediate-level radioactive waste) under alkaline conditions occurs via two main processes: a peeling-off reaction and a basecatalyzed cleavage of glycosidic bonds (hydrolysis). Both processes show pseudo-first-order kinetics. At ambient temperature, the peeling-off process is the dominant degradation mechanism, resulting in the formation of mainly isosaccharinic acid. The degradation depends strongly on the degree of polymerization (DP) and on the number of reducing end groups present in cellulose. Beyond pH 12.5, the OH^- concentration has only a minor effect on the degradation rate. It was estimated that under repository conditions (alkaline environment, pH 13.3-12.5) about 10% of the cellulosic materials (average DP = 1000-2000) will degrade in the first stage (up to 10⁵ years) by the peeling-off reaction and will cause an ingrowth of isosaccharinic acid in the interstitial cement pore water. In the second stage (10⁵-10⁶ years), alkaline hydrolysis will control the further degradation of the cellulose. The potential role of microorganisms in the degradation of cellulose under alkaline conditions could not be evaluated. Proper assessment of the effect of cellulose degradation on the mobilization of radionuclides basically requires knowing the concentration of isosaccharinic acid in the pore water. This concentration, however, depends on several factors such as the stability of ISA under alkaline conditions, sorption of ISA on cement, formation of sparingly soluble ISA-salts, etc. A discussion of all the relevant processes involved, however, is far beyond the scope of the presented overview.     

Rheological Investigation of Wood-Polypropylene Composites in Rotational Plate Rheometer

In this research work, the rheological properties of Wood-Plastic Composites (WPC) with some selected compositions are investigated. WPC is being recognized as a green composite that, in the past 20?years, has emerged to a commercial product. A study on rheological properties of these materials can give insight into the proper selection of composition and processing condition. Two grades of polypropylene (PP) with two different melt flow indexes (MFI) were selected to prepare WPCs with three different wood contents (50, 60 and 70?% wt.). Four types of rheological experiments were performed utilizing a rotational plate rheometer: (1) strain sweep, (2) frequency sweep, (3) temperature sweep and (4) steady shear rate sweep. The independent variables were chosen as wood content, MFI of polymer (two types), melt temperature, frequency or shear rate, the gap between the plates, and strain percentage. The strain sweep tests specified the linear and non-linear viscoelastic zones of each experiment. The results of frequency sweep experiments indicated that increasing the wood content and frequency and also decreasing the strain percentage and the gap distance, lead to an increase in the storage modulus. Regarding the loss modulus, wood percentage and the gap distance presented positive effects and strain percentage showed a negative effect. The behavior of complex viscosity was almost similar to that of the storage modulus but increasing the frequency caused a decrease in the complex viscosity. In case of temperature sweep experiments, it was observed that the rheological properties exhibit a rapid change near to a temperature of 160?°C. The results also showed that beyond this point, increasing the wood content and also MFI of polypropylene caused an increase in the storage modulus. The results of steady shear rate sweep experiments specified that increasing wood content and also decreasing the MFI of PP, the gap distance and shear rate lead to an increase in both viscosity and shear stress.     

Biodegradable Poly(lactic acid) Blends with Chemically Modified Polyhydroxyoctanoate Through Chain Extension

Poly(lactic acid) (PLA) was blended with chemically modified Polyhydroxyoctanoate (mPHO) using a Haake twin-screw mixer. Due to the melt viscosity disparity between the two components, PHO was reacted with Hexamethylene diisocyanate (HDI) used as a chain extender to produce high molecular weight for improving compatibility and processability with PLA. The number average and weight average molecular weight of the PHO, reacted with 0.55 wt% HDI, were increased 314 and 275%, respectively, compared with those of the unmodified PHO. The blends were characterized for rheological, thermal, and mechanical properties. Infrared spectra confirmed the formation of the urethane linkages in mPHO. The shear viscosity, as a function of shear rate or shear stress, decreased with an increase in mPHO content, indicating that the PLA/mPHO blends show shear-thinning behavior along with the power-law model. DSC thermograms showed that the two components in the blends were found with two crystalline phases and two amorphous phases confirming the coexistence of two immiscible components. Tensile results indicated that tensile strength for blends decreased with increasing mPHO content up to 80%. A decrease in elastic modulus, as well as an increase in elongation at break, was seen as a function of mPHO content. Results of aging tests showed that the mechanical properties of the blends also dropped more at a higher PLA level when compared with those of the unaged samples.     

Application of Cellulose Microfibrils in Polymer Nanocomposites

Cellulose microfibrils obtained by the acid hydrolysis of cellulose fibers were added at low concentrations (2–10% w/w) to polymer gels and films as reinforcing agents. Significant changes in mechanical properties, especially maximum load and tensile strength, were obtained for fibrils derived from several cellulosic sources, including cotton, softwood, and bacterial cellulose. For extruded starch plastics, the addition of cotton-derived microfibrils at 10.3% (w/w) concentration increased Young’s modulus by 5-fold relative to a control sample with no cellulose reinforcement. Preliminary data suggests that shear alignment significantly improves tensile strength. Addition of microfibrils does not always change mechanical properties in a predictable direction. Whereas tensile strength and modulus were shown to increase during addition of microfibrils to an extruded starch thermoplastic and a cast latex film, these parameters decreased when microfibrils were added to a starch–pectin blend, implying that complex interactions are involved in the application of these reinforcing agents.     

Rheological study of biodegradable blends of starch and polyvinyl alcohol

The rheological behavior of biodegradable blends of starch and poly(vinyl alcohol) (PVOH) was measured as a function of temperature, shear rate, and moisture content using a capillary rheometer. An excellent correlation was found with a rheological model which was used as a means to characterize the influence of starch/PVOH content as well as a qualification of the viscosity for simulation studies. This model consisted of a power law dependence on shear rate, an Arrhenius dependence on temperature, and an exponential dependence on moisture.Paper presented at the Biodegradable Materials and Packaging Conference, September 22–23, 1993, Natick, Massachusetts.Guest Editor: Dr. Randall Shogren, USDA.     

Lignocellulosic Fiber-Reinforced Keratin Polymer Composites

Short fiber reinforced polymer composites were prepared from lignocellulose fibers and feather keratin polymer (FKP). The FKP matrix was prepared from the reactive processing of poultry feather keratin, glycerol, water, and sodium sulfite. Lignocellulose fibers of varying source, length, and mass fraction were used and it was found that positive reinforcement of FKP was affected by all three. Positive reinforcement was defined as an increase in elastic modulus when normalized by FKP with the same amount of glycerol but no fibers. Positive reinforcement was only able to occur for modulus but not stress at break indicating that the composites were of high physical properties only under small deformations. At large deformations, fiber pull-out was observed in the composites using scanning electron microscopy. The most likely origin of this behavior appeared to be from weak fiber–polymer interactions dominated by friction and rationalized by a force balance across the fiber–polymer interface. High fiber loadings were shown to be reinforcing because of the formation of a network of lignocellulose fibers. The addition of lignocellulose fibers increased the thermal stability of the material.     

Improving the Rheological and Mechanical Properties of Recycled PET Modified by Macromolecular Chain Extenders Synthesized by Controlled Radical Polymerization

In this work, a series of reactive copolymers of glycidyl methacrylate (G), styrene (S) and acrylonitrile (AN), were synthesized through reversible addition-fragmentation chain transfer polymerization and evaluated as macromolecular chain extenders in reactive extrusion of recycled poly(ethylene terephthalate) (rPET). The results obtained indicate that the addition of the reactive copolymers as chain extenders modifies the chain conformation in rPET causing low crystallization rate and low crystallinity. The physical and rheological properties (melt flow and intrinsic viscosity) of chain-extended rPET improved, rendering better processability. rPET modified with polymeric chain extenders shows improved rheological properties (complex viscosity, storage and loss modulus) and also displays higher elongation at break and impact properties as the GMA content in the chain extenders increase.     

Utilization of Porous Carbons Derived from Coconut Shell and Wood in Natural Rubber

The porous carbons derived from cellulose are renewable and environmentally friendly. Coconut shell and wood derived porous carbons were characterized with elemental analysis, ash content, X-ray diffraction, infrared absorbance, particle size, surface area, and pore volume. The results were compared with carbon black. Uniaxial deformation of natural rubber (NR) composites indicate the composites reinforced with the porous carbon from coconut shell have higher tensile moduli at the same elongation ratio than the composites reinforced with wood carbon. 40 % coconut shell composite showed a fivefold increase in tensile modulus compared to NR. Polymer–filler interactions were studied with frequency dependent shear modulus, swelling experiments and dynamic strain sweep experiments. Both linear and non-linear viscoelastic properties indicate the polymer–filler interactions are similar between coconut shell carbon and wood carbon reinforced composites. The swelling experiments, however, showed that the polymer–filler interaction is greater in the composites reinforced with coconut shell instead of wood carbon.     

Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate)/Polylactide Blends: Thermal Stability,Flammability and Thermo-Mechanical Behavior

Blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polylactide (PLA) with different PHBV/PLA weight ratios (100/0, 75/25, 50/50, 25/75, 0/100) were prepared by melt compounding. Their mutual contributions in terms of thermal stability, flammability resistance, mechanical properties and rheological behavior were investigated. The study showed that the increase in PLA content in PHBV/PLA blends leads to enhanced properties. Consequently, thermal stability and flammability resistance were improved. Further, the rheological measurements indicated an increase in storage modulus and loss modulus of PHBV matrix by addition of PLA.     

Rheological Behavior Under Shear and Non-Isothermal Elongational Flow of Biodegradable Polymers for Foam Extrusion

The production of many items, in particular for food packaging applications, is based on foam extrusion and thermoforming. These operations require the use of polymers which can grant some specific rheological properties, both under shear and elongational flow. In this work, the behavior of some biodegradable polymers [Mater-Bi^® and poly(lactic acid)] under shear and non-isothermal elongational flow was investigated and compared with a traditional, non-biodegradable polymer, in order to assess their suitability for industrial-scale foam extrusion and thermoforming. The rheological characterization evidenced the differences between the different biodegradable polymers and the reference polystyrene (PS), as well as the effect of humidity on their main rheological properties. This can be of great interest in helping to find an optimum solution in replacing PS for the production of food packaging items.     

Thermal, Mechanical and Rheological Behavior of Poly(lactic acid)/Talc Composites

In the present study, influence of talc on thermal, mechanical and rheological behavior of PLA is investigated and the structure?Cproperty correlation for the PLA/talc composites is established. Poly(lactic acid)/talc composites are prepared by melt mixing of PLA with talc in twin screw extruder followed by blown film processing. Various characterizations techniques are used to evaluate thermal, morphological, mechanical and rheological behavior of PLA/talc composites and its blown film. DSC analysis showed that degree of crystallinity of PLA/talc composites was higher than that of neat PLA because of nucleating ability of talc. Spherulite morphology of PLA/talc composites showed that talc has increased nucleation density of spherulite having smaller radius than that of neat PLA. Talc is effective in enhancing tensile modulus and storage modulus of PLA due to reinforcing ability of talc particles.     

Thermal and mechanical properties of poly(lactic Acid) and poly(ethylene/butylene Succinate) blends

In this study, blends of poly (lactic acid) (PLA) with poly(ethylene/butylene succinate) (Bionolle) have been investigated for their thermal and mechanical properties as a function of the concentration of Bionolle. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile tests were used to characterize the blends. From the results of the DMA and DSC, it was found that this blend system was not miscible within the compositions studied. DSC results showed that adding Bionolle aids in crystallization of PLA. It was observed that increasing the Bionolle concentration led to a slight increase in the strain-at-break of the blends but a decrease in the Young’s modulus and ultimate tensile strength. Biaxially oriented films showed an increase in tensile strength, modulus, and strain-at-break.     

Starch-Based Polymers in Extrusion Coating

The starch-based polymers exhibited shear thinning and elastic nature in rheological characterizations. Thin coatings with narrow neck-in could be produced at fairly high extrusion coating line speeds. Adhesion between the starch-based polymers and paperboard was typically weak. Water vapor barrier of starches was very poor. Soft starch grades had a good pinhole resistance and a good heat sealing performance. Brittle nature of starch caused cracking as the coated paperboards were creased.     

Desiccation of contaminant barrier materials amended with aqueous carboxymethyl cellulose solution

The stabilization potential of negatively charged sodium carboxymethyl cellulose (CMC) solution was assessed through investigation of its retention on clays under environmental conditions that promote soil desiccation. Sodium montmorillonite and kaolinite, commonly used in clayey soils, were mixed with aqueous CMC solutions in concentrations ranging from 0 to 10 g/L. These samples were dried in a specially-designed desiccation chamber which was operated at a temperature of 25°C and relative humidity of 30%. The results show an inverse proportionality between liquid loss and CMC concentration. Liquid loss from clayey soil follows the first-order reaction with a rate constant in the range of 4.6–6.7 mg/h. CMC half-lives on sodium montmorillonite during desiccation ranged from 103 to 181 h for an aqueous concentration range of 0.5–10 g/L compared to 108 h for distilled water. For kaolinite, more liquid was retained at 10 g/L CMC concentration than at other concentrations, but liquid retention was generally insignificant. These conclusions are valid for a desiccation duration of 890 h, a time that is reasonably simulative of the duration of exposures of bare ground surfaces to weather elements. The experimental results are explained in terms of the role of CMC molecular interactions with clay minerals in controlling fluid flow to desiccating clay surfaces.     

Thermal Stabilization of Recycled PET Through Chain Extension and Blending with PBT

This study investigates the effect of using a multifunctional epoxide chain extender (Joncryl^® ADR 4468) on the thermal stabilization and rheological properties of recycled polyethylene terephthalate (R-PET) and its blends with polybutylene terephthalate (PBT). The R-PET samples were prepared without and with chain extender (CE) contents of 0.4 wt% and 0.8 wt%. R-PET/PBT blends with weight ratios of 75w/25w, 50w/50w and 25w/75w were also prepared without and with a given CE content of 0.2 wt%. The thermal stability of the melt blended samples was analyzed through small amplitude oscillatory shear (SAOS) rheological experiments. The structure of the samples was evaluated using a Fourier transform infrared (FTIR) spectrometer. While the dynamic rheological properties of R-PET were improved with the addition of Joncryl and by blending with PBT, during the SAOS rheological experiments, the complex viscosity of R-PET further increased due to the concurrent polycondensation of R-PET and the resumption of Joncryl reaction with R-PET molecules. These reactions during the rheological experiments were further expedited with increasing the testing temperature. On the other hand, in R-PET/PBT blends, the reactivity of Joncryl was more noticeable in blends with higher R-PET contents due to the higher available internal reactive sites of much shorter R-PET molecules. It was observed that the addition of only 0.2 wt% Joncryl to the blends of R-PET/PBT (75w/25w) dramatically improves the thermal stability and dynamic rheological properties of R-PET and most likely its processability.

     

Thermal,Rheological, Mechanical and Morphological Behavior of High Density Polyethylene and Carboxymethyl Cellulose Blend

In this study water soluble sodium carboxymethyl cellulose (CMC) was blended with high density polyethylene (HDPE) by peroxide-initiated melt compounding technique. The compatibility of the blended polymers were carried out by silane crosslinking agent. A series of blends were prepared by varying the CMC contents up to a maximum of 50 phr. The physical properties of non-crosslinked and crosslinked blends were investigated in detail. FTIR analysis of crosslinked blend confirmed the presence of Si–O–Si and Si–O–C absorption peaks at 1050 and 1159 cm^?1. Thermal stability of crosslinked blends improved as compared to its non-crosslinked congener. Rheological study of crosslinked blends illustrated high complex viscosity and dynamic shear storage modulus. The tensile strength of virgin polyethylene was 8.1 MPa whereas the maximum tensile strength of 19.6 MPa was observed in crosslinked blend. Similarly lower deformation was observed in crosslinked blends under static load. Scanning electron microscopy of crosslinked formulations also showed strong adhesion between the polymers interface. The compatibility of HDPE and CMC is attributed to both free radical and condensation reactions.