The effect of degree of branching on the rheological and thermal properties of hyperbranched aliphatic polyethers

A series of hyperbranched aliphatic polyethers with different degree of branching (DB) and molecular weights have been studied with respect to their rheological and thermal properties. The DB was shown to affect the ability of the polymers to crystallize and thereby also the rheological properties of the polymers. A low DB resulted in semi-crystalline polymers with melting points between 100 and 130°C. The polymers with a higher DB were essentially amorphous and behaved as non-entangled Newtonian liquids in the molten state.     

Investigation of the relationships between the chain organization and rheological properties of atactic poly(vinyl alcohol) hydrogels

The structure and rheological behavior of atactic poly(vinyl alcohol) (a-PVA) hydrogels prepared by freeze/thaw cycles were investigated as a function of polymer concentration and number of freeze/thaw cycles. The presence of phases with different mobilities was observed using ¹³C CP/MAS and DP/MAS NMR experiments. The degree of crystallinity of the a-PVA-rich phase was determined by ¹H NMR free decay experiments. Measurements of the shear storage and loss modulus were performed at a fixed frequency of 1 Hz and a strain value of 0.1%, i.e. under conditions where the deformation imposed on the gel structure is entirely reversible. Results thus obtained showed that an increase in the number of freeze/thaw cycles induces an increase in the degree of crystallinity in the polymer-rich phase together with an increase in the storage modulus. The a-PVA hydrogels became more fragile as the number of freeze/thaw cycles was increased. Moreover, both the percentage of protons in a rigid environment measured by ¹H NMR and the storage modulus values tended to a limiting value after six freeze/thaw cycles. These results show that the first five or six freeze/thaw cycles play a very important role in determining the hydrogel structure and rheological properties. A more detailed comparison of NMR and rheological data led to the conclusion that the storage modulus is mainly controlled by the a-PVA crystallinity while the hydrogen bond interactions have a much smaller contribution.     

Impact of additives on the rheological properties of associating water-soluble multiblock polyelectrolytes

The impact of additives on the rheological behavior of four associating water-soluble multiblock polyelectrolytes previously synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization was described. These polyelectrolytes contained different number of blocks ranged from 1 to 7 divided into hydrophilic and hydrophobic. The rheological analyses of polymers were performed at 25°C at a given concentration (0.1–15 wt%) in the presence of sodium chloride (NaCl) 0.1–0.5 M, sodium dodecyl sulfate (SDS) 2–10 mM or a mixture of both. Data demonstrated an increase in the viscosity of macroRAFT (ɳ = 0.002–9 Pa·s) and triblock copolymer-TBC (ɳ = 0.003–0.04 Pa·s) versus the concentration of NaCl. Meanwhile, the viscosity of penta and heptablock copolymer exhibited a diminution whatever the (NaCl) used. Results from the rheological analyses of the associative polyelectrolytes at different (SDS) revealed that the viscosity of macroRAFT and triblock copolymer was kept constant in spite of the increment of the (SDS) while the viscosity of PBC and HBC displayed a pronounced diminution at the lower (SDS). Finally, the results from the rheological analyses of these polyelectrolytes versus a mixture of NaCl-SDS showed a diminution in the viscosity of these solutions at any concentration of additives.     

Thermal dehydroxylation of clay as alternative to organic modification: effects on properties of nanocomposites

Abstract

This study presents a novel approach towards clay modification via thermal dehydroxylation, for polymer nanocomposite application. The feasibility of modification of clay via thermal dehydroxylation and its influence on the polymer properties was investigated, with reference to the polyproplylene (PP) nanocomposites. In spite of ample available literatures on organophillic clay/polymer composites, use of organic compound for the clay modification has been found detrimental in various aspects. Therefore, in order to corroborate the advantage of the thermal dehydroxylation method over organophillic modification, a comparative aspect of the effect of the organically modified and thermally dehydroxylated clay on the polymer properties has been established. Wherein, remarkably greater mechanical, dynamic mechanical, thermal and microstructural properties were noticed in case of nanocomposites reinforced with thermally dehydroxylated clay. Modification of clay via thermal dehydroxylation method was found to be an effective approach for polymer nanocomposite application.     

添加剂对炭/石墨复合材料性能的影响

以酚醛树脂为黏结剂,石油焦、石墨为原料,分别添加磷酸氢二钠、硼酸、碳化硅,在1 100℃下热处理,制备出炭/石墨复合材料,并考察了其机械性能、微观结构和热性能。研究表明:经过焙烧后,炭/石墨复合材料中的添加剂起到增强颗粒间键合能力,提高炭/石墨复合材料机械强度的作用。同时,硼酸、碳化硅可以在炭/石墨复合材料表面形成抗氧化物质,使其具有更好的抗氧化能力,起始氧化温度提高180℃,终了氧化温度提高了200℃。     

The effect of copolymer composition on the surface properties of perfluoroalkylethyl acrylates

The surface properties of two perfluoroalkylethyl acrylic copolymers—aqueous, Zonyl^®329 and solvent‐based, Zonyl^®225—were studied. Zonyl^®329 is a water‐based dispersion and Zonyl^®225 a solvent‐based copolymer solution; both polymers have the same perfluoroalkyethyl side chains [F(CF₂)_nCH₂CH₂? ] but have different comonomer compositions. Thin films, prepared by dip coating onto mica and quartz, with and without annealing, were characterized by contact angle and by X‐ray photoelectron spectroscopy (XPS). The contact angle measurements showed little variation with polymer and with substrate, consistent with the supposition that the perfluoroalkylethyl chains aggregate on the surface and thus dominate surface properties, irrespective of the composition of the rest of the polymer. XPS revealed only small variations in surface chemistry for studied films. Annealed films showed improved segregation for solvent‐based Zonyl^®225, which has both hydrocarbon alkyl and perfluoroalkylethyl side chains; the presence of hydrocarbon alkyl chains enables the perfluoroalkylethyl chains to reorganize after annealing. Depending on the external conditions, this thermal treatment can enable more perfluoroalkylethyl chains to reach the film surface (solid/air interface), leading to a reduction in the dispersive‐dominant surface and enhancement in perfluoroalkylethyl segregation. This suggested that perfluoroalkylethyl side chains dominate the surface properties, which are thus not dependent on substrate, backbone composition, or formulation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

An investigation on the rheological and sulfur-retention characteristics of desulfurizing coal water slurry with calcium-based additives

Desulphurizing coal water slurry is a kind of new clean coal water slurry(CWS), which has good performance on SO₂ emission during combustion and gasification process. But, the addition of sulfur-retention agents have some effects on the stability and fluid characters of the coal water slurry. In this paper, the viscosity, stability and rheology of Xinwen coal water slurry have been studied by adding different kinds of calcium-based sulfur-retention agents and different dosage. The results show that the sulfur-retention agents have little effect on rheological nature of CWS, which still presents pseudoplastic fluid. The addition of sulfur-retention agents will increase the viscosity of CWS, but the stability will decrease a little. The results also show that inorganic calcium has less negative effect on the performance of CWS than the organic calcium. The viscosity of the CWS with organic calcium agent keeps 1000–1200 mPa s when Ca/S molar ratio is 2. Sulfur release of the CWS with CaCO₃ reduces to 52% at Ca/S = 2 compared to original of 98%.     

Effect of dispersing and stabilizing additives on rheological characteristics of the upgraded brown coal water mixture

Upgraded brown coal water mixture (UBCWM) preparation by using an Indonesian upgraded coal produced by upgraded brown coal (UBC) process, was carried out to study the effect of dispersing and stabilizing additives on rheological behavior of the UBCWM. Three kinds of anionic dispersing additives, naphthalene sulfonic formaldehyde condensate (NSF), poly (meth) acrylate (PMA) and poly styrene sulfonic acid (PSS) and three kinds of stabilizing additives, carboxyl methyl cellulose (CMC), rhansam gum (S-194) and gellan gum (S-60) were used in this study. Results indicate that the addition of NSF 0.3 wt.% together with S-194 0.01 wt.% is effective in preparing UBCWM with good slurryability and stability, based on its rheological characteristics with the apparent viscosity at shear rate of 100 s^− 1 and yield stress at zero point of shear rate. The rheological behavior of all of the UBCWM that prepared, exhibits non-Newtonian Bingham plastic. From the economical point of view, the price of S-194 is expensive. On the other hand, CMC is cheap and abundant. Therefore, the addition of CMC 0.01 wt.% together with NSF 0.3 wt.% is also effective in preparing UBCWM with good fluidity and stability.     

Study of the rheological properties and solution microstructure of progressively cross-linked aqueous gels

A stepwise cross-linking polyacrylamide hydrogel was prepared using the laboratory homemade stepwise crosslinker PVC-PP-Cr and partially hydrolyzed polyacrylamide. The microstructure was investigated by using the scanning electron microscope and dynamic light scattering. The results show that the system has a controllable cross-linking time of 4 ~ 6 h, good heat resistance, and maximum gel strength of >300,000 mPa.S. In terms of viscoelastic behavior, a stepwise cross-linking process between crosslinker and hydrolyzed polyacrylamide (HPAM) is presented, and the viscoelasticity is increased step by step. During the stepwise cross-linking process, the dendritic structure, network structure and lamellar structure to a stable spatial network structure is obtained. Here, the cross-linked structure between polymer molecular chains is formed after addition of the crosslinker, which increases the steric hindrance of macromolecular chains and further enhances the stability of the system. With the gradual release of chromium ions from the PVC-PP-Cr stepwise crosslinker, the gel system is formed continuously. When intermolecular friction stopped increasing, intermolecular entanglement and interaction are enhanced, and elasticity is also increased.     

The effect of carboxylic acids and phosphate salts additives on the properties of chondroitin sulfate calcium phosphate cements

The use of liquid phase additives is a strategy to improve the physicochemical, mechanical, and biological properties of calcium phosphate cements. In this study, TTCP and α-TCP particles were synthesized using the solid-state reaction method. Apatite cements were prepared by mixing TTCP/DCPD/α-TCP powders and liquid phases containing chondroitin sulfate with various additives of carboxylic acids and phosphate salts. The formation of hydroxyapatite and consumption of raw materials as well as the acceleration and deceleration periods through cementation process were investigated by XRD and DSC experiments, respectively. In addition, the morphology, setting time, porosity, compressive strength, degradation, in-vitro bioactivity and cytotoxicity were studied. The results showed that the approximate amount of hydroxyapatite resulting from the cementation process was divergent in the presence of liquid phase additives. The use of phosphate salt additives presented better results compared to carboxylic acid ones regarding hydroxyapatite cement product formation, compressive strength, hardening, setting, and cytotoxicity. All cements showed, generally a similar tendency to form dense hydroxyapatite on their outer surfaces through immersion in the simulated body fluid. The cement containing Na₂HPO₄ salt exhibited the lowest cytotoxicity and highest strength. The ALP assay and the morphological behavior of MG63 cells indicated the good activity and proper cell adhesion of this cement.     

Effect of various superplasticizers on the rheological properties of Portland cement pastes

In the present work, the influence of the addition of some superplasticizers employed for maximising the solid loading of Portland cement pastes has been investigated. Cement pastes were prepared from deionized water and a commercial manufactured ordinary Portland cement 32.5 R (produced by Buzzi Unicem). Cement and water were mixed with a vane stirrer according to ASTM Standard C305. The water/cement ratio was kept fixed at 0.32. Three commercial superplasticizing agents produced by Ruredil were used: they are based on a melamine resin (Fluiment 33 M), on a modified lignosulphonate (Concretan 200 L), and on a modified polyacrylate (Ergomix 1000). Rheological tests were carried out at 25 °C by using the rate controlled coaxial cylinder viscometer Rotovisko-Haake 20, system M5-Osc., measuring device MV2P with serrated surfaces. The tests were performed under both continuous and oscillatory flow conditions. Ergomix 1000 presents a different behaviour as that of the other two superplasticizers studied, because it shows a marked shear-thickening behaviour above a critical deflocculant concentration and slight elastic effects particularly at high dosages as well.     

Influence of molecular architecture and melt rheological characteristic on the optical properties of LDPE blown films

A systematic investigation on the origin of the haze of LDPE blown films was conducted, aiming to correlate the film haze with the molecular architecture and melt rheological properties. First of all, the haze measurement indicated that the surface haze, rather than the bulk haze, is the dominating factor for the total haze of the investigated films. No spherulitic crystals or other superstructures were observed for the LDPE blown films, implying that the crystallites formed in the film-blowing process are too small to be responsible for the optical haze. Rheological study revealed that the surface roughness was originated from the irregular flow of LDPE melt during the extrusion process. NMR, GPC and parallel-plate rheology were applied to study the molecular architecture of the LDPE resins. It was found that the LDPE sample with higher haze value exhibits distinctly larger portion of higher molecular weight component, broader molar mass distribution, significantly higher side chain branch density.     

Influence of particle size and fluid fraction on rheological and extrusion properties of crosslinked hyaluronic acid hydrogel dispersions

Crosslinked hyaluronic acid (HA) hydrogels are widely used in gel/HA fluid formulations as a viscosupplement to treat joint diseases; thus, it is important to characterize these hydrogels in terms of their particle size and to investigate the effects of the gel/fluid mixtures on their rheological properties and extrusion force. Hydrogels previously crosslinked with divinyl sulfone were sheared in an Ultra‐Turrax unit to produce particles with mean diameters ranging from 20 to 200 μm. Hydrogels with 75–100 μm mean diameters were also evaluated in dispersions containing a 20–40% mass fraction of HA fluid. The mean diameters were measured by laser light scattering and the rheological behavior was determined by oscillatory and steady measurements in parallel plate geometry. The HA hydrogels exhibited the typical behavior of so‐called weak gels, as analyzed by the storage and loss moduli G′ and G″, respectively. The viscoelasticity, the viscosity, and the extrusion force increased with the hydrogel particle size. The fluid phase dispersions decreased both moduli. At 40% fluid fraction, the gel characteristics were lost and the dispersion behaved as a fluid. Based on these results, the particle size and HA fluid fraction in hydrogel dispersions may be optimized to develop more efficient viscosupplement formulations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of time addition of superplasticizers on the rheological properties of fresh cement pastes

It is well known that the fluidity and the fluidity loss of fresh cement pastes are affected by the kind and the time of addition of organic admixtures. The influence of the time addition of two chemical admixtures, namely, melamine formaldehyde sulfonate (MFS) and naphthalene formaldehyde sulfonate (NFS), on the rheological properties of ordinary Portland and sulfate-resisting cement pastes through the first 120 min of hydration was investigated. The admixture addition was delayed by 0, 5, 10, 15, 20, and 25 min. Shear stress and apparent viscosity of the cement pastes were determined at different shear rates (3-146 s⁻¹) and hydration times of 30, 60, 90, and 120 min. The concentration of Ca²⁺ and the combined water content of the cement pastes were determined after 120 min. Yield stress and plastic viscosity values were also determined by using the Bingham model. The results show that an increase in the addition time of the admixture reduces the shear stress, the yield stress, and the plastic viscosity of the cement pastes at the early ages (15 min) as well as at later early ages (120 min). The optimum delaying time of admixture addition is found to be 10-15 min. This time does not depend on the cement and superplasticizer type.     

Effects of a strong polyelectrolyte on the rheological properties of concentrated cementitious suspensions

Strong polyelectrolytes, referred to as superplasticizers, are known to improve the initial fluidity of concentrated cement suspensions. To quantify how the polyelectrolytes affect the fluidity, we have studied the effect of a strong anionic polyelectrolyte, melamine formaldehyde sulfonate (MFS), on the zeta potential of cement particles and on the steady-shear and low-amplitude rheological properties of cement suspensions. Adsorption of low concentrations of MFS onto the cement particles leads to an inversion in the sign of the surface potential, causing the electrostatically flocculated particles to become electrostatically dispersed and giving rise to a corresponding decrease in the steady-shear viscosity and storage modulus. At an intermediate MFS concentration, the steady-shear viscosity and the storage modulus each display a minimum. This concentration corresponds to that at which the zeta potential becomes constant. Larger concentrations of MFS result in an increase in the viscosity and storage modulus, which is attributed to depletion flocculation. These results thus relate the interaction between particles to the suspension fluidity through the analysis on the surface potential of particles and microstructure of suspension.     

The effect of additives on the properties of phosphate-bonded corundum refractories

Conclusions The composition was developed for a corundum refractory, the characteristics (other than the chemical and mineral compositions) and metal resistance of which are on the level of those of an imported tested refractory.A phosphate binder reduces the porosity and increases the strength, thermal-shock resistance, and metal resistance of corundum brick.Added zircon and kyanite-sillimanite concentrates and ZrO₂, whether stabilized with yttrium oxide or unstabilized, affect the metal resistance of the refractory adversely but added B₂O₃ does not.Translated from Ogneupory, No. 3, pp. 41–46, March, 1977.     

添加物对氮化硼材料性能的影响

研究了引入锆英石和氧化铝等添加物的热压氮化硼材料的抗氧化性、热震稳定性及力学性能。结果表明，向氮化硼中引入锆英石和氧化铝后，虽然未能按预期设想生成莫来石，但却对提高氮化硼材料的抗氧化性、热震稳定性及力学性能有利。     

The influence of surface-modified graphites on the rheological pattern of alumina-carbon cementitious refractory castable matrix

The present contribution focused mainly on the fundamental understanding of the influence of surface-modified graphite on rheology of the matrix of a castable slurry in comparison to the same containing the uncoated one. A special observation on the rheology of a graphite-free matrix of similar high alumina castable has been described. The change in rheological behavior due to the presence of other microfine constituents has also been noticed with a particular attention to the refractory cement bond. The variation in viscosity and shear stresses with shear rate of castable matrices containing as-received and surface-modified graphites has been compared. The ‘ball-in-hand’ consistency test of respective castables had also been differentiated. The effect of coated and uncoated graphites on the loss and storage moduli of the respective suspensions has been explored. Zeta potential values of individual constituents as well as the slurries have also been measured and correlated with the flow characteristics of castable matrices. The X-ray diffraction (XRD), SEM (scanning electron microscope) and EDS (energy dispersive spectroscopy) studies of the coated graphite have been observed to substantiate the flow pattern of the slurry. The physical properties of refractory castables at different temperatures have been estimated to supplement the rheological pattern.     

The effect of SEBS on interfacial tension and rheological properties of LDPE/PS blend

The effects of SEBS as a compatibilizer on the interfacial tension and rheological properties of LDPE/PS blend have been studied. Interfacial tension was measured by the breaking thread method. The measured interfacial tension of the LDPE/PS blend was 8.26 dyn/cm. It decreased rapidly with SEBS contents to 1 wt % and then leveled off to a saturation value, 3.6 dyn/cm. Dynamic oscillatory shear, elongational viscosity, and recovery after elongation were measured as the rheological properties. Storage modulus at low frequencies decreased with SEBS contents to 1 wt %. More addition of SEBS, however, increased the storage modulus at low frequencies. Similar behaviors could be observed in elongation viscosity and recovery after elongation. Hardening of elongational viscosity and recovery after elongation were reduced with 1 wt % SEBS, and they enhanced again with more SEBS contents. This means that there is a critical concentration of SEBS that acts as a compatibilizer and reduces the interfacial tension. More SEBS than the critical concentration saturates the interface and increases the elasticity of the LDPE/PS blend, while maintaining the interfacial tension between LDPE and PS constant. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 905–911, 2005     

新型高流动聚丙烯注塑专用料分子量及流变性能研究

对由聚合得到的新型高流动聚丙烯注塑专用料M#的热稳定性、分子量及流动性进行了系统的表征,井与国外样品AP03B和M1600进行了比较.结果表明;M#和AP03B、M1600的热稳定性相似,起始分解温度304℃,最大热失重温度458℃.重均分子量及分子量分布的大小顺序为:M#＞AP03B＞M1600.熔体流动速军(MFR)大小顺序为AP03B＞M1600＞M#.在高温下,剪切速率(γ)将对M#的加工性能有较大影响.