The influence of core-shell structured modifiers on the toughness of poly (vinyl chloride)

The core-shell structured grafted copolymer particles of polybutadiene grafted polymethyl methacrylate (PB-g-PMMA, MB) were prepared by emulsion polymerization. The MB particles were used to modify poly (vinyl chloride) (PVC) by melt blending. The mechanical properties of the PVC blends were investigated. The micro-morphology of the PVC blends was observed by scanning electron microscopy (SEM). The results indicated that the samples with the best impact strength could be obtained when the core-shell weight ratio of PB to PMMA is lower than 93:7, the mechanical properties correlated well with SEM morphologies, the addition of modifier with the ratio core to shell of 93:7 could reduce the domain size of the dispersed phase. Furthermore, the compatibility and properties of the blends were greatly enhanced and improved. The modifier particles could be well dispersed in the PVC matrix.     

Charged patch attraction in dispersion: effect of polystyrene sulphonate molecular weight or patch size

The molecular weight (Mw) effect of polystyrene sulphonate (PSS) on the yield stress of ZrO₂ dispersion was evaluated. Three “monodispersed” samples with Mw of 1430, 9960 and 130,000, and two broad distribution samples of Mw 70,000 and 1.0 million were investigated. Adsorbed PSS gave rise to charged patch attraction that enhanced the maximum yield stress, τ _{y max}, of dispersions at charge neutral condition [3]. As a PSS patch consists of only one molecule, the patch size should increase with increasing Mw. For PSS of Mw 1430 with just only seven repeating units the patch formed would be rectangular (linear) and small with a high charge density. For Mw of 9960 and higher, the patch would be irregular in shape with a smaller charge density. At a moderate surface coverage of ˜20%, the τ _{y max} increases quite sharply from Mw 9960 to 130,000 and very gradually from 130,000 to 1.0 million. From Mw 9960 to 130,000, the strength of the patch attraction increases quite strongly with increasing patch size. From Mw 130,000 to 1million, the small increase in τ _{y max} reflected a limiting patch size effect. At the limiting size, the attraction is at maximum strength. At the same coverage, PSS of Mw 1430 also displayed a strong charge patch attraction. This was attributed to a higher number of charged patch interactions at the closest point of separation and also to the high charge density of the PSS patch. The low surface coverage of 6% revealed no significant molecular weight effect on τ _{y max}. The network structure consisted of a mixture of charge patch and bare surface interactions. Received: 4 July 2000/Accepted: 18 July 2000     

Interparticle forces arising from an adsorbed strong polyelectrolyte in colloidal dispersions: charged patch attraction

Adsorbed polystyrene sulphonate (PSS) shifts the pH of the zero zeta potential, pH_ς = 0, of ZrO₂ to a lower pH. The positive charge density of ZrO₂ at pH = pH_ς=0 determined from the amount of PSS adsorbed was in excellent agreement with that obtained from charge titration. Polystyrene sulphonic acid shifts pH_ς=0 to a greater degree compared with polyacrylic acid because it is a much stronger acid. A patch is likely to just consist of one adsorbed molecule. The patch is negative when the charges of the molecule exceed the underlying positive surface charge. Attraction between the negative patch and the bare positive surface of a second particle is responsible for increasing the yield stress of concentrated ZrO₂ dispersions at pH_ς=0. Its magnitude is only of the order of the van der Waals attraction. Increasing ionic strength and patch misalignment diminish the attraction. The upper limit of the patch area was estimated from the radius of gyration of the molecule in solution. With a known patch area, the patch charged density can be calculated. With the selection of an appropriate patch area, the yield stress due to charged patch attraction increases linearly with the product of the negative and positive patch densities. Received: 30 March 1998 Accepted: 18 September 1998     

Effect of low frequency ultrasound on the surface properties of natural aluminosilicates

Structural and surface properties of different natural aluminosilicates (layered, chain and framework structural types) exposed of 20 kHz ultrasound irradiation (0–120 min) in aqueous and 35 wt%. aqueous H₂O₂ dispersions were studied by X-ray diffraction (XRD), dynamic light scattering (DLS), nitrogen adsorption–desorption, thermal analysis, and Fourier transform infrared spectroscopy (FTIR) techniques. It was confirmed that sonication caused slight changes in the structure of investigated minerals whereas their textural properties were significantly affected. The aqueous dispersions of montmorillonite (Mt), clinoptilolite (Zlt), glauconite (Glt) and palygorskite (Pal) were represented by several particles size fractions according to DLS-study. Ultrasound irradiation produced a decrease of the average particle diameter by 4–6 times in water and by 1.3–5 times in H₂O₂ dispersions except for Pal, which underwent strong agglomeration. A significant increase of total pore volume and pore diameter was observed for Glt sonicated in H₂O₂ dispersions whereas for Pal mainly micropore volume sharply increased in both aqueous and H₂O₂ dispersions.     

The effects of cis–trans configuration of cyclohexane multi-carboxylic acids on colloidal forces in dispersions: steric, hydrophobic and bridging

The effects of cis- and trans-1,2-, trans-1,4-cyclohexanedicarboxylic acid, 95% cis-1,3,5-cyclohexane tricarboxylic acid and cis-1,2,3,4,5,6-cyclohexanehexacarboxylic acid on the yield stress–pH behaviour of concentrated ZrO₂ dispersions are reported. Adsorbed cis-1,2,3,4,5,6-cyclohexanehexacarboxylic acid imparts predominantly steric interactions. It forms a steric barrier keeping the interacting particles apart. Adsorbed cis- and trans-1,2 increase the maximum yield stress and this was attributed to a hydrophobic force resulting from the part of the cyclohexane ring sticking out into the solution which is devoid of charged or hydrophilic group. Adsorbed trans-1,4 increases the maximum yield stress by at least threefold and its configuration favours strong bridging interaction with an adjacent particle. Predominantly, cis-1,3,5 also increases the maximum yield stress but only by 60% at the same additive concentration. This was attributed to a smaller degree of bridging.     

Small angle neutron scattering studies on non-aqueous dispersions of calcium carbonate. Part III. Concentrated dispersions

Small angle neutron scattering has been used to examine calcium carbonate dispersions in toluene over the w/w concentration range 5 to 40 %. The particles were stabilised by a combination of a surface active agent and a linear polymeric molecule. Analysis of the experimental data gave results for the structure factorS(Q) and the pair correlation functiong(r).Theoretical computations of the structure factor were made using a hard sphere model and the mean spherical approximation approach. These analyses indicated that the interaction was essentially soft at low volume fractions but became hard at the higher volume fractions.     

Shear thickening in electrically-stabilized colloidal suspensions

A theory is presented for the onset of shear thickening in colloidal suspensions of particles, stabilized by an electrostatic repulsion. Based on an activation model, a critical shear stress can be derived for the onset of shear thickening in dense suspensions for a constant potential and a constant charge approach of the spheres. Unlike previous models, the total interaction potential is taken into account (sum of attraction and repulsion). The critical shear stress is related to the maximum of the total interaction potential scaled by the free volume per particle. A comparison with experimental investigations shows the applicability of the theory.     

Characterization of polymer dispersions by Fourier transform rheology

Fourier transform rheology is a very sensitive technique to characterize non-linear rheological fluid properties. It has been applied here for the first time to polymer dispersions in water and the results are compared to those from conventional rheology, namely steady and small amplitude oscillatory shear experiments. The investigated systems are mainly based on styrene and n-butylacrylate. A first attempt was made to evaluate how far colloidal parameters like particle volume fraction and ionic strength as well as chemical composition and surface characteristics of the dispersed particles are reflected in FT-rheology spectra. Significantly different non-linearities are observed for highly concentrated dispersions of particles with different T_g. These differences are not detected in linear oscillatory shear and show up in steady shear only at significantly higher shear rates. Particle surface characteristics influence the non-linear response in oscillatory shear significantly and the intensity of the overtones is found to be higher for a dispersion of particles with a “hairy” swollen surface layer as compared to a system of smooth particles, although the solids content was adjusted to match the steady shear viscosity. The intensity of the overtones in FT-rheology strongly decrease upon dilution. At a solid content below 35% no differences are observed in the FT-experiments for the systems investigated here, whereas the differences in steady shear are very pronounced in this concentration range. A significant influence of added salt onto the non-linear response is detected for some systems, which might be correlated to the stability of these systems. The observed phenomena certainly cannot be explained in terms of constitutive equations or microstructural statistical mechanical models at present. Thus, FT-rheology yields information complementary to classical steady or linear oscillatory shear experiments. Received: 11 December 2000 Accepted: 8 April 2001     

Rheology as a tool for the analysis of the dispersion of carbon filler in polymers

The aim of this work is to validate the use of dynamic oscillatory measurements in the melt to characterize the dispersion of a filler in a matrix after melt blending. Polyethylene oxide (PEO) is used as a polymeric matrix. Active carbon is used as a filler at a constant filler volume content of 26.4%. The melt viscosity of the polymeric matrix is varied by melt blending of two miscible POE and polyethylene glycol (PEG) species having very different molecular weight distributions. This enables to obtain various matrix viscosities and in turn various states of dispersion of the filler that were characterized by optical microscopy and image analysis. Dynamic mechanical measurements in the melt in the terminal zone show a large increase of the moduli associated to the presence of the filler. Comparison with the results of optical microscopy shows that this increase is clearly related to the dispersion. The interparticle distance is likely to be the leading parameter rather than the number of particles. Characterization of the amount of bound polymer shows that the amount of bound polymer is nearly independent of the matrix composition. Futhermore, the composition of the bound layer reflects the matrix composition though PEO is slightly preferentially bound on the active carbon.     

Studies on Separation of Liquid‐Liquid Dispersions: Diesel‐Water System in Batch Settler

In this article, batch settling of liquid‐liquid dispersion in a vertical batch settler was comprehensively studied. The experiment results of the investigation on liquid‐liquid batch settler phase separation were compared with a well predefined physical model proposed by Jeelani and Hartland [1998, Ind. Eng. Chem. Res. 37: 547–554] using a semi theoretical approach. The effect of initial dispersion height, initial hold‐up volume, settler diameter, and mixing time on separation of batch liquid‐liquid dispersions were experimentally investigated in terms of variation in the final settling time and coalescing interfaces with time. From the present work it was found that, final separation time varied as polynomial function of degree 2 with respect to initial dispersion height and was constant with respect to initial hold‐up volume. Final separation time also varied according to the completeness of dispersion achieved with respect to the mixing time. The experimental data obtained showed a good correlation with the theoretically predicated values. Results allow the use of experimental procedure with the mathematical model as a tool in monitoring the dispersion behavior in commercial units on industrial importance.