RHEOLOGICAL CHARACTERIZATION OF PROCESSABILITY OF UNVULCANIZED POLYBUTADIENE

Rheological investigation on a series ot unvulcamzed polybutadiene elastomers of different processability has been carried out by means of a capillary extrusion rheometer. It is found that the processability of unvulcanized polybutadiene can be correlated with the occurrence of unsteady flow and the wall stress, dependence of the dimensionless number e characterizing the entrance elongational elasticity which has been found to be sensitive to the branching structure and the molecular weight distribution of the samples. Interpretations based on the structural data of unvulcanized polybutadiene were discussed.     

Shear flow experiments in an assembly of gel beads and modelling of bingham behavior

In this paper, we present a rheological study of a compact layer of highly swollen gel beads. The flow regimes of these systems are modelled by an elastic sinusoid moving in a Newtonian fluid. This model predicts a yield stress varying with the square root of the elastic modulus of the gel bead. The slope at the origin (at zero velocity) of the flow curve is expected to depend only on geometrical parameters and on the solvent viscosity. The experimental data are in qualitative agreement with the theoretical predictions.     

Transient rheological behavior of lyotropic (acetyl)(ethyl)cellulose/m-cresol solutions

The chiroptical properties and transient rheological behavior of (acetyl)(ethyl)cellulose (AEC) m-cresol liquid crystalline solutions have been investigated. Chiroptical properties were manipulated through (i) increasing degree of acetylation of ethyl cellulose (EC), and (ii) blending AEC with EC. At the same average degree of acetylation (DA), the chiroptical properties of pure AEC were different from those of the EC/AEC mixtures. However, at the same DA, the AEC and mixed AEC/EC solutions showed similar steady state flow and oscillatory behaviors, but the transient behaviors were different. At high flow rates the mixed AEC/EC solutions exhibited double recoil after cessation of steady-state flow, whereas the AEC solutions showed double recoil only in the high DA AEC solutions. All solutions, pure and mixed, had the same stress relaxation behavior. Both pitch and handedness affected the transient behavior. After cessation of high shear rate flow, the rate of modulus evolution decreased with increasing pitch, and was faster in right-handed mesophases than in left-handed ones at a similar pitch.     

Influence of hydrophobe content on the solution rheology of hydrophobically modified terpolymer of SO2, N,N-diallyl-N-carboethoxymethylammonium chloride

Rheological properties of hydrophobically modified copolymer of SO₂, N,N-diallyl-N-carboethoxymethylammonium chloride and the hydrophobic monomer N,N-diallyl-N-octadecylammonium chloride were studied. The influence of hydrophobe content (HP) and polymer concentration was investigated. Polymers with HP content in the range 1.5-5% were examined and the concentration was varied in the range 2-5 wt%. Both dynamic and steady-shear experiments were performed in ARES rheometer. Copolymers were observed to exhibit typical viscoelastic behavior even with low HP content. Both the dynamic viscosity, η′ and storage modulus, G′, increase with the increase of both the polymer concentration and the HP content of the system. The viscosity of the high HP content polymer showed a strong shear dependency, while G′ was a weak function of frequency and gel-like behavior was observed. The zero-shear viscosity, η₀, showed a strong concentration dependency (η₀ ∼ ?^α; 1.1 < α < 5.9). The concentration dependency of η₀ suggests that intermolecular association is dominant in the high HP content polymer. Control of the HP content and polymer concentration of this class of polymers can lead to a wide range of interesting rheological properties.     

Rheology of asphalts modified with glycidylmethacrylate functionalized polymers

Asphalt is known to be a colloidal suspension in which asphaltenes are covered by a stabilizing phase of polar resins and form complex micelles that are dispersed in the oily maltenic phase. In order to enhance its mechanical properties (e.g., in road paving), asphalts are often loaded with polymeric materials, thereby obtaining blends that can have different physical or chemical structures, depending on the composition of the added polymer. Asphalts modified by the addition of reactive ethylene terpolymers were prepared and their dielectric and rheological properties were measured both before and after a cure at high temperature. Even if it is not possible to determine the exact nature of the chemical interactions between asphalt and polymer, master curves obtained from dynamic data clearly show that during the cure the material tends to the behavior of a cross-linked network.     

Concentrated reverse micelles in a random graft block copolymer system: structure and in-situ synthesis of silver nanoparticles

The structure and rheological properties of a poly(dimethylsiloxane)-graft-poly(oxyethylene) copolymer at high concentrations in block-selective solvents were studied by small-angle X-ray scattering (SAXS) and rheometry. Analysis of SAXS data indicates that quasispherical, reverse micellar aggregates (with no ordered packing) are present in concentrated solutions of the copolymer in nonpolar solvents, and that upon addition of water, the size of such aggregates increases due to the solubilization inside the micellar cores. The viscosity of concentrated polymer solutions increases exponentially as water is added, and finally, viscoelastic, gel-like behavior is found in the vicinity of the phase separation limit. It was found that small silver nanoparticles with an average diameter of ≈3 nm can be synthesized inside the copolymer aggregates without the need of a reducing agent; namely, particles embedded in a viscoelastic matrix are obtained. The synthesis seems to follow first-order kinetics. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Development of new lubricating grease formulations using recycled LDPE as rheology modifier additive

The recovery of plastic waste but also its applicability in product development may be an incentive to industry, since the use of such plastics represents a cheaper source of raw material. The aim of the present paper is to study the feasibility of recycling polyolefins as additives to improve the rheological properties of lithium 12-hydroxystearate lubricating greases. The effects that both soap and recycled low-density polyethylene (LDPE) concentration exert on the rheology of lithium lubricating greases and its relationship with grease microstructure are discussed in this work. In this way, different lubricating grease formulations were manufactured by modifying the concentration of lithium 12-hydroxystearate and content of recycled LDPE, according to a RSM statistical design. These lubricating greases were rheologically characterized through small-amplitude oscillatory shear (SAOS) and viscous flow measurements. In addition to these, scanning electronic microscopy (SEM) observations and mechanical stability tests were also carried out. Recycled LDPE was found to be an effective additive to modify grease rheology, acting as filler in the soap entangled microstructure. The values of both apparent viscosity and viscoelastic functions in the linear viscoelastic region increase with soap and recycled polymer concentrations. However, the addition of recycled LDPE distort the microstructural network of these greases resulting greases with less relative elastic characteristics and poorer mechanical properties as LDPE content increases.     

Investigations on the recycling of hemp and sisal fibre reinforced polypropylene composites

Microscopic, mechanical, rheological and thermal tests were carried out in order to determine the recycling behaviour of PP/vegetal fibre composites. Different composites using hemp and sisal were characterized. All results were compared with PP-g-MA/hemp composites and PP/glass fibre composites.The results prove that mechanical properties are well conserved with the reprocessing of PP/vegetal fibre composites but that there is poor adhesion between the fibres and PP without any treatment. The addition of PP-g-MA shows an improvement of the bonding evidenced by MEB pictures. Vegetal fibres induce an increase in the percentage of crystallinity χ_c and in the crystallization temperature T_c which can be explained by the nucleating ability of the fibres improving crystallization of PP. The Newtonian viscosity η₀ decreases with cycles, indicating a decrease in molecular weight and chain scissions induced by reprocessing. The decrease of fibre length with reprocessing could be another reason for viscosity decrease.     

ELECTRO-OPTICAL DETERMINATION OF α-FeOOH PARTICLE SIZES

Electric light scattering method is used for revealing the presence of aggregates in very diluted aqueous α-FeOOH suspensions. Three theoretical models are used for the geometrical form of aggregates. The comparison between the electro-optical results -theoretical and experimental - shows that even in the most diluted suspensions exist aggregates with irregular form. Using the comparison between electron microscopy and electro-optical results the geometric shape of the aggregates is determined.