Thickening Properties Research Articles

Steady and Dynamic Shear Rheological Properties of Gum-Based Food Thickeners Used for Diet Modification of Patients with Dysphagia: Effect of Concentration

Gum-based food thickeners are widely used for diet modification for patients with dysphagia in Korea. In this study, the rheological properties of two commercially available gum-based food thickeners (xanthan gum and xanthan-guar gum mixture) marketed in Korea were determined as a function of concentration. The steady and dynamic shear rheological properties of the food thickeners in water were investigated at five different concentrations (1.0%, 1.5%, 2.0%, 2.5%, and 3.0% w/w). Both food thickeners showed high shear-thinning fluid characteristics (n=0.14-0.19) at all concentrations (1.0-3.0%). In general, the thickener with the xanthan-guar gum mixture showed higher values for steady shear viscosity compared to that with xanthan alone, whereas it showed lower dynamic rheological parameter values. Steady and dynamic rheological parameters demonstrated differences in rheological behaviors between the gum-based food thickeners, indicating that their rheological properties are related to the type of gum and gum concentration. In particular, the type of gum played a role in the time-dependent flow properties of the gum-based food thickeners. Appropriately selecting a commercial food thickener appears to be of great importance for dysphagia therapists and patients.

Rheological behavior of an acrylamide-based terpolymer with p-vinylbenzyl-terminated octylphenoxy poly(ethylene oxide)

A comb-like associating terpolymer PAOE was synthesized from acrylamide (AM), sodium 2-aciylamido-2-methylpropane sulphonate (NaAMPS) and a novel macromonomer: p-vinylbenzyl-terminated octylphenoxy poly(ethylene oxide) (VOE, degree of polymerization: 4—using aqueous free-radical copolymerization technique. The polymer chains were still comparatively extended in the brine solutions at low polymer concentrations. This leaded to the formation of continuous network structures via the intermolecular hydrophobic associations of the octylphenyl groups in despite of the addition of NaCl. As a result, PAOE predominantly exhibited significant elastic characters in brine solutions at 0.5–9 g/dL NaCl, as well as in aqueous solutions. The viscous and elastic character decreased slightly with increasing temperature from 25 to 45°C for the PAOE brine solution with 0.5 g/dL NaCl. The PAOE aqueous and brine solutions displayed obvious shear thickening behavior upon consecutive steady shear cycles. The brine solution also showed the excellent thickening properties, salt-thickening behaviors twice, and resistance to salt.

Flow Behaviors of Commercial Food Thickeners Used for the Management of Dysphagia: Effect of Temperature

Gum-based food thickeners are widely used to care for patients with dysphagia in Korea. In this study, the flow properties of commercially available gum-based food thickeners marketed in Korea were determined as a function of temperature. The flow properties of thickeners were determined based on the rheological parameters of the power law and Casson models. Changes in shear stress with the rate of shear (1-100 s-1) at different temperatures (5, 20, 35, and 50 oC) were independent of the type of thickener. All thickeners had high shear-thinning behavior (n=0.08-0.18) with yield stress at the different temperatures tested. In general, apparent viscosity (na,50) values progressively decreased with an increase in temperature. In addition, the consistency index (K) and Casson yield stress (σoc) values did not change much upon an increase in temperature from 5 to 35 oC, except for sample B. In the temperature range of 5-50 oC, the thickeners followed an Arrhenius temperature relationship with a high determination coefficient (R2=0.93-0.97): activation energies (Ea) for the flow of thickeners were in the range of 2.44 - 10.7 kJ/mol. Rheological parameters demonstrated considerable differences in flow behavior between the different gum-based food thickeners, indicating that their flow properties are related to the type of thickener and the flow properties of gum.

Medium optimization and properties of biopolymer Ss from Sphingomonas sanxanigenens

Sphingomonas sanxanigenes strain NX02 synthesizes a novel biopolymer Ss, which can be extracted from fermentation broth using a low-cost acid precipitation. In this study, response surface methodology was employed to optimize medium composition for the production of biopolymer Ss. First, Plackett-Burman design was applied to evaluate the effects of different components in the medium, and it was found that glucose, MgSO4, and NaNO3 signii¬cantly ini¬‚uence the production of Ss. Central composite design was then used to optimize the concentrations of these three variables. As a result, the maximum Ss production was 17.5 g/L, which was 25% higher than that obtained using the original medium. In addition, biopolymer Ss has excellent thickening, shear thinning, gelling, and emulsification properties. Key words: Sphingomonas sanxanigenens, biopolymer, fermentation, optimisation and viscosity.

Polymerization of Micro-Block Associative Polymer with Alcohol-Surfmer Mixed Micellar Method and Their Rheological Properties

In this paper, mixed micelle composed of alcohol and polymerizable surfactant (surfmer) were constructed. The aggregated numbers of surfmer (hexadecyl trimethyl allylammonium chloride (C16DMAAC)) in the mixed micelle were measured using a steady-state fluorescence quenching (SSFQ) technique. Using a mixed micellar method with adiabatic polymerization and post-hydrolyzation techniques, the high molecular weight (Mw) micro-block associative polymer of P(AM-NaAA-C16DMAAC) was polymerized. Structures were characterized by Fourier transform-infrared (FT-IR) spectroscopy and 13 C nuclear magnetic resonance (NMR) spectroscopy. Using rheological experiments, the effects of micro-block length and salt concentration of on the thickening and viscoelastic rheological properties of the polymers were studied. All experiments confirmed that the micro-block length could be adjusted using the mixed micellar method. Increases in the micro-block length were accompanied by decreases in the critical associative concentration (CAC). The viscosities and viscoelastic rheological properties increased to maximum then decreased steady with the length increasing, indicating that the length was at an optimum value.

Association in Unsalted and Brine Solutions of a Water-Soluble Terpolymer with p-Vinylbenzyl-Terminated Octylphenoxy Poly(ethylene oxide)

An associating terpolymer (PAOE) of acrylamide (AM), sodium 2-acrylamido-2-methylpropane sulphonate (NaAMPS), and a novel macromonomer: p-vinylbenzyl-terminated octylphenoxy poly(ethylene oxide) (VOE, degree of polymerization: 4) was synthesized by aqueous free-radical copolymerization. The PAOE polymer exhibited excellent thickening properties in unsalted and brine solutions. The electrostatic shielding of repulsive interactions of the polymer was much weaker than that of the linear associating polymers with small hydrophobic monomers. This brine solution exhibited unexpected salt-thickening behaviors twice, and good resistance to salt and ageing. The intermolecular hydrophobic association in unsalted and brine PAOE solutions, as functions of polymer and NaCl concentration, were characterized by fluorescence spectroscopy. With the addition of NaCl, the polymer chains were comparatively extended and continuous network structures were formed via the intermolecular hydrophobic association in brine solutions as well as in unsalted solutions at 0.15–0.25 g⋅dL−1 PAOE, as observed by a scanning electron microscope (SEM).

Thickening and Rheological Properties of Crystalline Polyester Used in Low Pressure Sheet Molding Compounds

Low pressure sheet molding compound (LPMC,1.0-3.0 MPa,95-103 ℃) is a new kind of thermosetting material with crystalline polyester as a physical thickenner.LPMC is different from conventional SMC using an earth oxide thickening agent (e.g.MgO) as chemical thickenner,it relies on the physical thickening of crystalline polyester.Crystalline polyester resin is the key material to mold LPMC parts.Currently there was no report about the thickening mechanism of crystalline polyester in LPMC.In this article,crystalline polyester resins,whose melting points were between 45 ℃ and 89 ℃,were synthesized by a two-step esterification.The melt points of crystalline polyesters are controlled by regulating the mol ratio of the two glycols and the two acids.And by means of varying the content of crystalline polyester resin,the thickening effect on resin paste is investigated.In addition,the thickening mechanism of crystalline polyester in LPMC was investigated by FTIR and DSC analysis.The effects of the diameters and viscosity of crystalline polyester on the rheological property and fiber distribution of LPMC sheets were studied,too.Results show that the thickening effect is excellent when the weight content of crystalline polyester resin is 3%.And there exists three kinds of functions acting in the process of thickening:swelling,hydrogen bonds and induction crystallization.During the preparing process of resin paste in LPMC,the temperature of resin paste must be kept at 90 ℃.In addition,crystalline polyester make LPMC have a perfect fluid property.When the viscosity of LPMC sheet is beyond 1 kPa s,the fiber orientation is not obvious.But when the viscosity of LPMC sheet is about 500 Pa s,the fiber shows a certain degree of orientation.Moreover the study of physical and chemical thickening mechanism of crystalline polyester and the rheological discipline of LPMC sheets in the hot mould will provide the researchers and enterprises with theory guidance.

Synthesis and solution properties of novel comb-shaped acrylamide copolymers

An amphiphilic macro-monomer of allyl polyoxyethylene-12 ether with butyl-end group (AE12B) was synthesized, and its chemical structure was characterized. AE12B and the other two macro-monomers with different hydrophobic and hydrophilic groups were copolymerized with acrylamide to prepare the novel comb-shaped acrylamide copolymer (CPAM) through aqueous free radical polymerization. The solution properties of CPAM with different side-chain lengths were studied and compared with those of partially hydrolyzed polyacrylamide (HPAM). The experimental results show that the obtained CPAM, compared to HPAM, exhibited a dramatic enhancement in the heat- and salt-resistant properties. In addition, the increase of the side-chain length and the amount of hydrophobic groups in the side-chain improved the thickening properties of CPAM solution under high temperature and high mineralization conditions. Among the investigated macro-monomers, AE12B was optimized for the enhanced thickening properties of the CPAM solution.

SEM Morphologies of a Water-Soluble Terpolymer with Vinyl Biphenyl in Aqueous and Brine Solutions

A terpolymer PAAP, synthesized from acrylamide (AM), vinyl biphenyl (VP), and sodium 2-acrylamido-2-methylpropane sulfonate (NaAMPS), exhibits intermolecular hydrophobically associating behavior in water and aqueous brine solutions. A scanning electron microscope (SEM) was used to observe the conformations of polymer chains and morphologies of their associating microstructures in pure water and in brine solutions. This was done to reveal the relevant relationships between solution properties and associated microstructures for the PAAP polymer in pure water and brine solutions, and the mechanisms for the previously reported viscoelastic behavior of PAAP solutions. Continuous supermolecular associating network structures are formed via strong intermolecular hydrophobic association of biphenyl groups in an aqueous 0.1 g⋅dL−1 PAAP solution, which leads to the excellent viscoelastic character of aqueous PAAP solutions. With increasing polymer concentration, the network structures of the polymer become much larger and more compact in aqueous solution, which results in the excellent thickening properties of their solutions. The SEM results reveal that the elongated conformations of molecular chains in aqueous PAAP solutions are favorable for intermolecular hydrophobic association. With the addition of NaCl, the associating network structures of PAAP are destroyed because of electrostatic shielding effects on the –\(\mathrm{SO}_{3}^{-}\) groups, and huge tree-like associated structures are formed. This results in a decrease in the solution viscosity and a loss of viscoelastic properties of PAAP solutions. However, with increasing NaCl concentration, the number and size of the aggregates increase, which results in the salt-thickening behavior of PAAP brine solutions.

Characterization of Acid-Extracted Pectin-Enriched Products Obtained from Red Beet (Beta vulgaris L. var. conditiva) and Butternut (Cucurbita moschata Duch ex Poiret)

Chemical and rheological characteristics of fractions enriched in soluble dietary fiber are reported. These fractions were obtained through acid hydrolysis of butternut (Cucurbita moschata Duch ex Poiret) and red beet (Beta vulgaris L. var. conditiva) cell wall enriched powders. Hydrolysis was performed using citric acid at different pH values and reaction times (2 and 3 h). Yields obtained for butternut fractions were between 21 and 28 g/100 g; for red beet, yields were 24 and 31 g/100 g for pH 1.5 and 11 and 17 g/100 g for pH 2.0 for previously mentioned times; in general, the increase of the yield was directly correlated with the decrease of pH and the increase of reaction time. Products enriched in low methoxyl pectins were obtained in all cases. At the lowest pH assayed, pectins were essentially constituted by homogalacturonan; a significant content of neutral sugars was determined at the higher extraction pH. Neutral sugars were constituted mainly by arabinose, galactose, rhamnose, and glucose in different proportions for each fraction; in general, butternut fractions showed high glucose contents. Flow behavior for 2.00% (w/v) aqueous systems of the different products was evaluated. Data obtained for fractions isolated at pH 1.5 fit to Herschel-Bulkley and Cross models while those isolated at pH 2.0 fit to Ostwald and Cross models. All samples showed low viscosity and, hence, poor thickening properties.

Solution microstructure of a micro-crosslinked acrylamide-based terpolymer

The hydrophobically associating copolymer poly (acrylamide/butyl styrene/sodium 2-acrylamido-2-methylpropane sulphonate) (PASA) is micro-crosslinked with a small amount of phenolic aldehyde (PL) to obtain the micro-crosslinked polymer PASA–PL with excellent liquidity and water solubility. After crosslinked, the critical association concentration of copolymer reduces in the brine solution with high NaCl concentration and PASA–PL displays much better thickening and anti-aging properties in brine solutions at low polymer concentrations. The contribution of micro-crosslink of PASA with PL to the associating structures is investigated by fluorescent probe and scanning electron microscope (SEM). The fluorescent probe results show that a large amount of hydrophobic microdomains with very strong non-polarity are formed because of greatly strengthened intermolecular hydrophobic association for the PASA–PL polymer in aqueous and brine solutions, and PASA and NaCl concentration greatly influence intermolecular hydrophobic association in PASA–PL brine solutions. SEM measurements show that continuous associative structures with huge sizes are formed in PASA–PL aqueous and brine solution.

Synthesis and Rheological Properties of Responsive Thickeners Based on Polysaccharide Architectures

New thermothickening copolymers were synthesized by grafting responsive poly(ethylene oxide-co-propylene oxide) [PEPO] onto three different polysaccharide backbones: carboxymethylcellulose [CMC], alginate [ALG], and carboxylated dextran [DEX]. The coupling reaction between carboxylic groups of biopolymers and the terminal amine of PEPO was activated at low temperature ( T < 10 degrees C) in water by using carbodiimide and N-hydroxysuccinimide. In these conditions it was shown that the formation of amide bonds strongly depends on the concentration of reactive groups, which is limited by the viscosity of the polymer sample. While a full conversion was obtained for the low molecular weight dextran, the efficiency of grafting remains low (between 30 to 40%) for CMC and alginate, which give a solution of high viscosity even at low concentration. When studied in the semidilute regime, all the copolymer solutions clearly exhibit thermothickening behavior with a large and reversible increase of viscosity upon heating. The association temperature and the gelation threshold were shown to depend on polymer concentration as it is expected from the phase diagram of PEPO precursor. Similarly, the influence of added salt on PEPO solubility in water has been used to control the self-assembling behavior of copolymer formulations. The relative comparison between the three copolymers reveals that the amplitude of the viscosity jump induced by heating mainly depends on the proportion of responsive material inside the macromolecular architecture rather than the dimensions of the main chain. The high increase of viscosity, which can reach several orders of magnitude between 20 degrees C and body temperature, clearly demonstrates the potentiality of these copolymers in biomedical applications like injectable gels for tissue engineering.

Rheological Evaluation of Silicon/Carbopol Hydrophilic Gel Systems as a Vehicle for Delivery of Water Insoluble Drugs

The present study analyzed the thickening properties of Carbopol 974 and 971 in a 50:50 mixture of water/Silsense A-21, a new cationic silicon miscible in any proportion with water. Samples were prepared by simply dispersing different Carbopol amounts (0.5-4%) at room temperature or at 70 degrees C without neutralizing. Temperature sweep and time sweep analysis did not reveal significant structural changes at increasing temperature in the samples prepared following the first procedure. On the other hand systems obtained at 70 degrees C possessed higher elastic character particularly at polymer concentration higher than 2% (w/v). Analysis of the G' and G'' vs frequency curves by using different fitting equations (linear fitting, power law) gave information about the viscoelastic properties of the systems. The fitting of the frequency spectra and the calculation of the relaxation times from the master curves outlined the structural differences within the samples prepared with the two different procedures, confirming stronger gel-like behaviour for the samples prepared by the heating procedure. High preparation temperature promoted the polymer-solvent interactions, aiding the solvation of Carbopol. Heating facilitated polymer-solvent and polymer-polymer interaction, giving rise to a better organised structure typical of gel-like systems. Furthermore this preparation method provided good stability properties as shown by the stress sweeps tests performed during the three months of storage. The interpretation of the rheological results was supported by statistical analysis. A design methodology (screening and optimisation) was also applied in order evaluate the influence on dynamic rheological moduli of several parameters (polymer type and concentration, preparation method, temperature of the tests). This last method showed the relevance of the interaction of two main factors: polymer concentration and preparation procedure. Thus, statistical analysis confirmed that temperature increased the polymer-solvent interaction and improved the viscoelastic properties of the systems, particularly when Carbopols were present in considerable amounts.

Acrylic polymers as thickening agents for tetraglycol cosolvent

This article evaluated the thickening properties of two different Eudragits, L and RS, in tetraglycol cosolvent in order to obtain high viscosity systems characterized by controlled release properties. Tetraglycol was chosen for its ability to dissolve a wide range of water insoluble drugs, while Eudragit RS and L for their specific dissolution and permeability properties under physiological conditions. Study of the rheological properties was performed to characterize elastic and viscous properties of Eudragit/tetraglycol samples in function of frequency and temperature. For all systems, the results outlined a liquid like behavior, as observed for dilute polymer solutions. In fact the fitting of the log G′-log G′′ versus frequency curves showed a good agreement with the Rouse or Zimm models. So despite the increase in viscosity, samples still behaved like liquid systems. After the addition of paracetamol the release characteristics were defined pointing out the great release control properties of both Eudragit L and RS, which showed different release kinetics depending on the pH of the environment. Semisolid Eudragits/tetraglycol systems can be considered as a new alterative for the sustained release of insoluble or poorly water-soluble drugs.

Perceived creaminess of semi-solid foods

Results of sensory, physiological and physico-chemical studies from our laboratory on perceived creaminess of semi-solids foods are reviewed. Most results stem from studies using model vanilla custard desserts, allowing systematic variation of fat, flavor and thickener properties. The generalizability of the custard results was verified for yogurts, mayonnaises, white sauces and other semi-solid foods. Creaminess sensations could be decomposed into sensations reflecting either properties of the bulk or of the surface of the oral food bolus. Bulk properties related to the rheological properties of the bolus whereas surface properties related to lubrication and flavor release. Creaminess was inversely related to enzymatic and mechanical induced break-down during oral processing. Starch thickeners generally enhanced creaminess although they suffered from enzymatic break-down compared to non-starch thickeners. It is suggested that the negative effects of break-down were off-set by positive effects of fat migrating to the surface of the bolus. The surfaced fat enhances lubrication and the release of fat-soluble flavors enhance creaminess, especially in low fat starch-based semi-solids. Bulk-related properties were measured by rheological measurements, surface-related properties were measured by friction, and mechanical- and enzymatic break-down properties were measured with a modified rheometer.

Physicochemical and rheological properties of thickeners produced from Tunisian clays

Modification of two samples of Tunisian clays of the type of natural smectites with organic derivatives of ammonium salts was studied. The physicochemical properties of the modified products and the possibility of their use as components of lubricating oils were analyzed.

W05K Tailored damping and self-repair of composite materials(International Workshop on "New Frontiers of Smart Materials and Structural Systems")

Composite materials are currently developed not only for their structural properties, but also because they are good candidates to integrate other materials or devices, which bring added functions to the part. Several examples are presented based on recent work performed at LTC, which cover the areas of damping and self-repair. Tailored damping has been addressed following two different routes: (i) active damping using Shape Memory Alloys (SMA) is made possible by embedding pre-strained SMA wires into a host material ; (ii) another route to damp some unwanted frequencies in a composite beam is to introduce a layer with shear thickening properties, which stiffens when the local shear exceeds a given level, without the need for an external energy source. Finally, recent research on self-repair of composites using embedded resin micro-capsules and SMA wires for closing cracks and heating the resin will be presented. In all these examples, manufacturing issues are addressed to bring these concepts closer to practical applications.

Novel Approach to Synthesizing Hydrophobically Associating Copolymer Using Template Copolymerization: The Synthesis and Behaviors of Acrylamide and 4-(ω-Propenoyloxyethoxy) Benzoic Acid Copolymer

Hydrophobically associating copolymers of acrylamide (AM) with a small amount of 4-(omega-propenoyloxyethoxy) benzoic acid (PEBA, <2.5%) were synthesized by template copolymerization in the presence of poly(allylammonium chloride) (PAAC) as a template in an aqueous medium. These template copolymers exhibited remarkable thickening properties due to the effective hydrophobic association, which were similar to those copolymers with a multiblock structure obtained by the micellar process. The pH of the reaction medium and the molecular weight of the template strongly influenced the thickening properties of the products. In the experimental range, the higher the PEBA content, the larger the thickening capacity of these hydrophobic copolymers. The aggregate behaviors of these copolymers were studied by fluorescence, transmission electron microscopy (TEM), and light scattering techniques. The apparent critical interpolymer aggregate concentration (cac) of the copolymer solution was about 0.5 g/dL. As the concentration of the copolymer became higher than the cac, the aggregates changed their morphology from small hollow spheres to big flower-shaped aggregates. All the above results indicated that the template copolymerization gave access to a very simple and powerful means for the preparation of hydrophobically associating copolymers and other functional polymer materials.

β-Lactoglobulin Gelation and Modification: Effect of Selected Acidulants and Heating Conditions

ABSTRACT: The effect of acidulant selection, heating temperature, and heating rate on the properties of low-pH β-lactoglobulin (β-Lg) gels and powders derived from these gels was investigated by rheological and microscopic techniques. As isothermal gelation temperature was increased from 75 to 85 °C, gels made with hydrochloric and lactic acid showed more rapid gel formation and increased stress at gel fracture. Thickening and water-holding properties of powders derived from these gels also increased with temperature. Increases in gel strength and derivatized powder functionality appeared to plateau above 85 °C. Gels and derivatized powders prepared with phosphoric acid exhibited attributes similar to samples prepared with HCl and lactic acid at lower temperatures. The ion-specific ability of phosphate to increase denaturation temperature was responsible for the shift in properties of gels made with phosphoric acid. Microscopy revealed temperature effects on network building block size, but variations in rheological properties could not be linked to changes in gel micrographs. Alteration of heating rates from 2.0 to 0.2 °C/min during gelation affected the observed gelation temperature, but had little effect on final gel mechanical properties. Acid selection and gelation temperature offer alternatives to control β-Lg gel strength and the functional properties of instant thickening protein ingredients.

Oxidative Reactions and Degradations of Sugars and Polysaccharides

AbstractFor Abstract see ChemInform Abstract in Full Text.