The influence of cosolvent polarity on the flow properties of hydroalcoholic gels: empirical models

The aim of this study was to investigate the influence of cosolvent polarity on the rheological flow properties of aqueous and hydroalcoholic gels obtained from the Carbopol Ultrez 10 base and used for topical applications. Specifically, we have examined the effect of pH (range 4.0--7.0) on the consistency and flow properties of dispersed systems in water and mixtures--15 : 85% v/v of methanol : water, ethanol : water, n-propanol : water and n-butanol : water--at a constant polymer concentration of 0.3% w/w. The gels, which had decreasing polarity values in the jellifying medium, showed qualitatively similar flow behavior, characteristic of pseudoplastic systems, and all of the flow curves were adjusted to the Ostwald model. Sigmoidal dose response functions were calculated to describe the flow and consistency indexes as a function of pH. As a result, the influence of alcohol polarity on the polymer network has been assessed meaningfully using the empirical parameters obtained: maximum consistency index value (k(max)), pH value required for 50% development of polymer network (pH(50)), and asymptotic flow index value (n(min)) for the fully structured gels.     

Effect of polymer entanglement on the toughening of double network hydrogels

The mechanical strength of double network (DN) gels consisting of highly cross-linked poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) as the first component and linear polyacrylamide (PAAm) as the second component has been investigated by varying the molecular weight of the second polymer PAAm, M(w). The experimental results reveal that, for toughening of the DN gels, (1) M(w) is one of the dominant parameters; (2) there is a critical value of M(w) = 10(6) for a remarkable enhancement; (3) the fracture energy of DN gels with a M(w) larger than 10(6) reaches a value as high as 10(3) J/m(2). By plotting the strength of DN gels (fracture stress sigma and fracture energy G) against a characteristic parameter of c[eta], where c is the average concentration of PAAm in the DN gels and [eta] is the intrinsic viscosity of PAAm, it is found that the dramatic increase in the mechanical strength of the DN gels occurs above the region where linear PAAm chains are entangled with each other. Thus, we conclude that the entanglement between the second component PAAm plays an important role of the toughening mechanism of DN gels. This result supports the heterogeneous model, which predicts the presence of "voids" of the first network PAMPS with a size much larger than the radius of the second polymer PAAm.     

Binary and ternary uranium(VI) humate complexes studied by attenuated total reflection Fourier-transform infrared spectroscopy

The complexation of U(VI) with humic acid (HA) in aqueous solution has been investigated at an ionic strength of 0.1 M (NaCl) in the pH range between pH 2 and 10 at different carbonate concentrations by attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. For the first time, the formation of binary and ternary U(VI) humate complexes was directly verified by in situ spectroscopic measurements. The complex formation constants for the binary U(VI) humate complex (UO(2)HA(II)) and for the ternary U(VI) mono hydroxo humate complex (UO(2)(OH)HA(I)) as well as the ternary U(VI) dicarbonato humate complex (UO(2)(CO(3))(2)HA(II)(4-)) determined from the spectroscopic data amount to log β(0.1 M) = 6.70 ± 0.25, log β(0.1 M) = 15.14 ± 0.25 and log β(0.1 M) = 24.47 ± 0.70, respectively, and verify literature data.     

Characterization of thermo-reversible gels by means of sedimentation equilibria

This paper describes the deformation of gels in a centrifugal field leading to a continuous equilibrium. A gel is considered to be a binary mixture of cross-linked polymer and solvent and is assumed to remain isotropic during the deformation. From the equation for the osmotically effective pressure, called swelling pressure, the thermodynamic properties of a gel can be calculated. For highly swollen gels the expression of Svedberg and Pedersen is obtained. It is shown that the complete concentration dependence of the swelling pressure in the concentration range of the maximally swollen gel up to that at the cell bottom can be measured in a single equilibrium experiment. The homogeneity of weakly cross-linked gels can be examined by means of the method described. Soluble parts which are not incorporated into the polymer network can also be detected if they are present. From the swelling pressure-concentration curves it is possible to derive the thermodynamic properties of the physically crosslinked gelatin/water gels that were investigated. These gels can be described by means of a slightly modified Flory-Huggins equation with an interaction parameter χw in the weight fraction scale, which depends linearly on concentration. The interaction parameters show a dependence on concentration which is explained by an increased branching and crosslinking of the polymer with increasing initial polymer concentration of the gels. At low initial polymer concentration, the primary chains have to aggregate to build up relatively long chains between the network junctions. The static shear modulus G which can be calculated from the network term has the same order of magnitude as the real part of the complex shear modulus which is measured at low frequency.     

Determination of fracture energy of high strength double network hydrogels

The fracture energy G of double network (DN) gels, consisting of poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) as the first network and poly(acrylamide) (PAAm) as the second network, was measured by the tearing test as a function of the crack velocity V. The following results were obtained: (i) The fracture energy G ranges from 10(2) to approximately 10(3) J/m2, which is 100-1000 times larger than that of normal PAAm gels (10(0) J/m2) or PAMPS gels (10(-1) J/m2) with similar polymer concentrations to the DN gels. (ii) G shows weak dependence on the crack velocity V. (iii) G at a given value of V increases with decreasing of cross-linking density of the 2nd network. The measured values of G were compared with three theories that describe different mechanisms enhancing the fracture energy of soft polymeric systems. A mechanism relating to a heterogeneous structure of the DN gel is convincing for the remarkable large values of G.     

Poly(N-acylethylenimine) copolymers containing pendant pentamethyldisiloxanyl groups. II. Thermal behavior and x-ray diffraction study

Two series of random copolymers of 10-(pentamethyl disiloxanyl) decyl oxazoline ( Si ) with undecyl ( U ) (four copolymer compositions) and nonyl ( N ) (eight copolymer compositions) oxazolines over the whole composition range, with a total degree of polymerization of about 100, were studied by DSC and wide angle X-ray diffraction. All the polymers are crystalline. For the N/Si copolymers, the melting points, normalized ΔH and ΔS of fusion are almost constant in a broad range of copolymer composition from 10 to 65 mol % of Si . The rationale for this behavior is that the copolymers crystallize two dimensionally, with the crystalline polymethylene plates separated by the bulky flexible pentamethyl disiloxanyl ( P ) groups. In this range, increasing Si only increases the distance between the plates. With more than 65 mol % Si , the bulky P groups interfere with the packing of the alkyl chains and change the crystallization behavior; the polymers show disordered packing as demonstrated by their X-ray patterns and extremely low ΔH. In the U/Si copolymers, since the undecyl side chain has one more carbon than the decyl group to which the P group is attached, the P groups interfere much more strongly with the packing of the side chains than in the N/Si polymers. The copolymer melting points uniformly decrease as the concentration of Si increases. The plateau on the plot of normalized ΔH versus polymer composition is only from 10 to 50 mol % of Si . The average long spacings of the annealed polymers increase linearly from 24 Å ( N/Si polymers) or 28 Å ( U/Si polymers) to 34.1 Å with the increase of Si up to 50%. With more than 50% Si , the polymers have an identical lamellar thicknesses of 34 Å, within the experimental error. Copolymers with less than 75 mol % of Si can crystallize from hexadecane solutions forming gels down to polymer concentrations of 2-3 wt %. The long spacings of the gels are almost identical with those of the pure crystalline polymers and independent of the polymer/solvent ratios. When hexamethyl disiloxane is added to the solutions, it can intercalate and the resulting crystalline gels have long spacings larger than those found in the absence of siloxane.     

Structural origin of the thixotropic behavior of a class of metallosupramolecular gels

Complexation, between a ditopic ligand, consisting of a 2,6-bis-(1′-methylbenzimidazolyl)-4-oxypyridine moiety (O-Mebip) attached to either end of a penta(ethylene glycol) core, with transition metal and lanthanide ions, results in the formation of metallosupramolecular polymers, soluble in acetonitrile at high temperatures. Cooling the hot sol to room temperature causes phase separation and crystallization, and produces mechanically-strong gels, which exhibit a highly thixotropic behavior. Optical microscopy indicates that the gel morphology consists of spherulitic particles, which are easily broken by mechanical shear. Reproducible gel properties are produced when the gel is formed by cooling in a sonication bath, which produces a finely-divided globular morphology, and increases the modulus of the gels. Wide angle X-ray diffraction study shows that the crystalline structures of the gels are strongly dependent on the thermal history of gel formation and the nature of the metal ion. The gel properties are a result of the interactions between the colloidal particles produced by the phase separation and crystallization process. These interactions, which may reflect electrostatic forces and possibly metal-ligand binding, in addition to the usual van der Waals interactions, give rise to the formation of a network structure. The disruption of this network by mechanical shear, and its facile reformation when shear is removed, are the origin of the pronounced thixotropic behavior of the gels.     

高机械性能的聚(丙烯酸-co-甲基丙烯酸十八酯)疏水缔合凝胶的溶胀行为研究

以丙烯酸(AA)、甲基丙烯酸十八酯(OMA)、十二烷基硫酸钠(SDS)为原料,采用胶束共聚的方法合成了疏水缔合(HA)凝胶.在HA凝胶内部,表面活性剂SDS与疏水单体OMA组成的增溶胶束起到物理交联作用,将亲水的聚合物链交联起来.通过单向拉伸试验证实了该凝胶具有较高的机械性能.此外,也测试了HA凝胶在不同pH值溶液中的溶胀行为.结果显示,HA凝胶具有特殊的溶胀行为,其溶胀过程可以分为凝胶溶蚀、溶胀平衡和凝胶瓦解3个阶段.在强酸性条件下,凝胶的溶胀被抑制,没有出现凝胶瓦解阶段.在强碱性条件下,凝胶的溶胀被促进,溶胀平衡阶段被越过.盐的存在也会抑制HA凝胶的溶胀,但在SDS溶液中,溶液中的SDS会促使凝胶中的疏水改性聚合物溶解到溶液中去,组成新的缔合结构,而使溶液增稠。     

An analysis of the swelling equilibrium of an ionic polymer network in a binary liquid mixture

An equation which represents the swelling equilibrium of an ionic polymer network in a binary liquid mixture is introduced and evaluated numerically. Discontinuous volume changes are obtained with pertinent values of the parameters. From two types of dependence of the degree of ionic dissociation on the composition of a liquid mixture, two types of volume transitions of an ionic gel are illustrated. One is the transition typically seen in acrylamide gels, and the other is a re-entrant transition typical of isopropylacrylamide gels. The selective dissolution factor of two liquids into a swollen polymer network also becomes discontinuous in accordance with the discontinuous volume change. Transition points and the spinodal line are calculated from a generalized form of the free energy change of the swollen gel system. © 1994 John Wiley & Sons, Inc.     

Fluorescence Correlation Spectroscopy Study of Probe Diffusion in Poly(vinyl alcohol) Solutions and Gels

In this study, we demonstrate how the diffusion of probe particles in aqueous poly(vinyl alcohol) (PVA) solutions and gels is affected by: (i) the presence of cross-links, (ii) the cross-link density, (iii) the polymer concentration. We apply fluorescence correlation spectroscopy (FCS) to measure the diffusion time of a rhodamine-based fluorescent particle (TAMRA) and TAMRA-labeled dextran in PVA solutions and gels prepared at various polymer concentrations (1% to 8.6% w/v) and cross-link densities (1/400 to 1/50 cross-link monomers per PVA monomers). The measurements indicate that the probe particles are slowed down with increasing polymer concentration and with increasing cross-link density. Also, FCS can detect differences in the diffusion times measured in “fresh” and “aged” PVA solutions. We find that FCS provides a quantitative measure of network inhomogeneities.     

Synthesis of polyacrylamide/polyurethane hydrogels by latex IPN and AB crosslinked polymers

Interpenetrating polymer network (IPN) and AB crosslinked polymer (ABCP) hydrogels composed of polyacrylamide (PAAm) and polyurethane (PU) have been synthesized as function of degree of polymerization of PU prepolymer, crosslink density of PAAm domain, and gel composition. Both PAAm/PU IPN and ABCP gels gave synergistic effects in terms of density showing positive deviation from the linear additivity. As a result of this, the strength of swollen gel increased over approximately two times with a small addition of flexible PU (10–20%) to the rigid PAAm.     

Kinetics of fluid spreading on viscoelastic substrates

The spontaneous spreading of non‐film‐forming fluids on the surfaces of aqueous solutions of poly(2‐acrylamido‐2‐methyl‐propanesulfonic acid) and its chemically crosslinked gels was studied. The experiments were performed in the same concentration range for the solutions and gels, far above the overlap concentration of the polymer solutions. The leading edge (R) of the spreading liquid showed a power‐law behavior with time t: R = K(t + c)^α, where α is the spreading exponent and K is the spreading prefactor. α and K were significantly different for the polymer solutions and gels. Here c was a constant that depended on the initial conditions of the spreading liquids. Depending on the polymer concentration, α of the polymer solutions varied between the upper (3/4) and lower (1/10) theoretical limits for viscose liquids and solids, respectively. This indicates that no universal scaling law exists for the spreading process on viscoelastic surfaces. On the polymer gels, which were elastic substrates, universal values of α could be observed and could be expressed as R ∝ (t + c)^0.45 and R ∝ (t + c)^0.3 for miscible and nonmiscible spreading liquids, respectively; they showed no dependence on the polymer concentration or network mesh size. This shows that on an elastic gel surface, spreading is more or less similar to that on a solid surface. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 562–572, 2005     

Physical organogels composed of amphiphilic block copolymers and 1,3:2,4-dibenzylidene-D-sorbitol

The 1,3:2,4-dibenzylidene-D-sorbitol (DBS) molecule is capable of self-organizing into nanoscale fibrils through intermolecular forces such as hydrogen bonding and pi interactions. At sufficiently high concentrations (typically less than approximately 2 wt%), the nanofibrils can form a network that promotes physical gelation of the matrix medium. Previous studies have investigated the mechanism of DBS-induced gelation and the features of DBS-containing gels in poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). In this work, we examine the effect of adding DBS to a series of amphiphilic PPG-b-PEG-b-PPG triblock copolymers differing in composition and molecular weight. Dynamic rheological measurements reveal that the resultant gels are thermoreversible (i.e., they exhibit comparable mechanical properties before dissolution and after reformation under quiescent conditions), exhibiting a maximum in the elastic modulus (G') at temperatures near the gel dissolution (T(d)) and formation (T(f)) temperatures. Both T(d) and T(f) tend to increase with increasing DBS concentration and PPG content, and their difference decreases with increasing PPG fraction in the copolymer. The magnitude of G' is sensitive to copolymer composition and polymer identity at low DBS concentrations, but becomes polymer-independent as the DBS network saturates at concentrations in excess of approximately 1 wt%.     

Rheological characterization of two viscosity grades of methylcellulose: an approach to the modeling of the thixotropic behaviour

The rheological behavior of two viscosity grades of methylcellulose (MC) (M-0262 and M-0512) was determined based on the dispersions of different polymer concentrations (from 0.1 to 5% w/w). In order to analyze the possible thixotropic character of the dispersions, the up and down curves of rheograms for several agitation times were plotted. In all cases, the Ostwald-De Waele rheological model (or Power Law model) was used. For both grades of MC, preparations of concentrations in the range of 0.1–1.0% (w/w) exhibited Newtonian behavior, while at polymer concentrations from 2–5% (w/w), pseudoplastic behavior was observed. The lower viscosity grade MC (M-0262) showed no thixotropy, while the higher viscosity grade MC (M-0512) exhibited thixotropic behavior from 2–5% (w/w). To analyze and define thixotropic behavior, we propose an equation model obtained from the values of consistence, m, determined for each of the curves in a flow diagram The results obtained from the proposed equation model showed good correlation to those obtained with the thixotropic areas method, and thus could be used as an alternative model for analyzing thixotropy.     

羧甲基纤维素钠/蒙脱土悬浮体系的流变性能及其影响因素

考察了蒙脱土(MT)质量分数(w)、羧甲基纤维素钠(CMC)/MT质量比(R)、电解质(NaCl、MgCl2和AlCl3)、pH值和温度对MT或CMC/MT悬浮体系流变性能和触变性的影响。 结果表明,随w增加,纯MT悬浮体系的流体类型由近牛顿流体向塑型流体变化,触变类型则由无触变、正触变向复合触变性转变;而CMC/MT悬浮体系仍保持MT体系的正触变塑型流体特征,但屈服值τ0和稠度指数K增加,滞后环面积S和电动电势|ζ|先增加后减小,表现出同步变化。 电解质和实验温度均不改变CMC/MT悬浮体系的正触变性塑型流体特征,但电解质使τ0和K增加,而温度增加使τ0和K减小。 随介质pH值的增加,CMC/MT体系由负触变性变为正触变性,|ζ|增大,S先增加后减小,且在pH=8.46时达到最大。     

Influence of polymer structure on the rheological behavior of hydroxypropylmethylcellulose–sodium carboxymethylcellulose dispersions

Aqueous dispersions of mixtures of hydroxypropylmethylcellulose (HPMC) and sodium carboxymethylcellulose (NaCMC) were prepared in accordance with a two-component simplex lattice design, using polymer varieties with different molecular weights and substitution characteristics. The resulting systems were characterized rheologically by capillary viscometry, flow rheometry, and oscillatory shear techniques, for the determination of kinematic viscosity, index of consistency, index of fluidity, elastic modulus, and viscous modulus. The values obtained for these parameters were fitted with appropriate canonical models, which revealed synergistic effects for some polymer proportions. Maximum synergy was observed when polymer proportions were optimal for the establishment of between-polymer interactions. The synergistic effects on viscosity and elasticity are attributable to the establishment of hydrophobic interactions and hydrogen bonds between HPMC and NaCMC chains, as revealed by IR spectroscopy and modifications in the cloud-point temperature. The observed among-mixture differences in the polymer proportions at which maximum synergy occurs, and the degree of this synergy, are explained by differences in molecular weights and substitution characteristics, and indeed the degree of synergy (as measured by interaction parameters from the fitted canonical models) showed strong dependence on these variables. Microviscosity values, derived from theophylline diffusion data for some of the mixtures, show that the crossover and chain expansion of the polymers in the mixtures (i.e. increased viscosity and elasticity) give rise to a three-dimensional network with greater mesh size and a more hydrophilic microenvironment, favoring solute mobility. Received: 17 July 2000 Accepted: 20 November 2000     

Gelation of cellulose nanocrystal suspensions in glycerol

Aqueous suspensions of cellulose nanocrystals (NCC) produced by sulfuric acid hydrolysis of natural cellulose fibres display a number of unique properties. In addition to forming equilibrium chiral nematic phases above some critical concentration, cellulose nanocrystal suspensions tend to gel or aggregate if the stability of the suspension decreases, for example because of a decrease in the surface charge density of sulfate ester groups, or a change in the properties of the suspending medium. Direct incorporation of unmodified nanocrystals into organic media usually leads to aggregation. We have found that it is possible to circumvent this difficulty and form clear thixotropic gels of unmodified NCC in glycerol, by careful evaporation of water from aqueous glycerol suspensions of NCC. The physical gels form at a fairly low (<3 wt%) concentrations of cellulose. The initial composition of the suspension, the temperature and rate of evaporation, and the time resting at room temperature all influence the formation of thixotropic gels. Desulfation of the acid-form nanocrystals, enhanced in the glycerol-rich suspensions, is shown to be a key step in this gelation process.     

Distinct kinetic pathways generate organogel networks with contrasting fractality and thixotropic properties

The kinetics of the isothermal transformation of sols, comprised of a low molecular-mass organogelator (LMOG) and an organic liquid, to their organogel phases have been followed by circular dichroism (CD), fluorescence, small angle neutron scattering (SANS), and rheological methods. The thixotropic properties (in the sense that severe shearing followed by rest lead to reestablishment of viscoelasticity) of the gels have been examined as well by rheological measurements. The compositions of the samples were either 5alpha-cholestan-3beta-yl N-(2-naphthyl) carbamate (CNC) in an n-alkane (n-octane or n-dodecane) or 3beta-cholesteryl N-(2-naphthyl) carbamate (CeNC) in ethyl acetate. Values of Df, the mass fractal dimension of the microcrystalline self-assembled fibrillar networks (SAFINs) in the gels, have been extracted from the kinetic data using a model developed by Dickinson (J. Chem. Soc., Faraday Trans. 1997, 93, 111). The Df values, 1.1-1.3 for the CeNC gels and 1.3-1.4 or 1.6-1.8 (depending on the temperature of incubation of the sol phase) for CNC gels, are consistent with the gel network structures observed by optical microscopy. In addition, comparison of the temperature dependence of both n (the Avrami component) and K (the Avrami "rate constant") for CeNC/ethyl acetate gelation with those reported previously for gelation of CNC/n-alkane sols demonstrate that the very small change of a single bond in CNC to a double bond in CeNC causes significant differences in their gelation abilities and gel properties. The rheological measurements on CNC/n-alkane gels with spherulitic SAFIN units, formed by incubation of their sols at < or =28 degrees C, indicate that they are thixotropic. Gels with the same chemical composition but formed by incubation of their sols at > or =30 degrees C, leading to fiberlike SAFIN units, remain liquidlike after shearing regardless of the periods they are at rest. The time-dependent viscoelastic properties of the gel networks are treated according to a stretched exponential model. The observations from these studies provide detailed insights into the mechanisms of formation of molecular organogel phases and demonstrate the extreme sensitivity of the SAFINs and viscoelastic properties of such organogels to slight modifications in LMOG structure or sample history.     

Composition of heteroassociates formed in HF-pyridine and HF-formamide binary liquid systems

The IR spectra and the densities of solutions in HF-pyridine and HF-formamide binary liquid systems were measured over a wide range of mole ratios HF: Solv (Solv is the organic solvent). The composition of heteroassociates (HA) formed in these systems was determined by analysis of the concentration dependences of normalized (to the total number of moles per 1 L) optical density in the IR region and the excess density of the binary mixtures under study. The HA with the stoichiometric ratio 3: 1 are present in the HF-Py system at all studied mole ratios of the components (from 1: 12 to 20: 1). The 1: 2 HA were found in the dilute solutions, whereas the >6: 1 HA were revealed in the concentrated solutions. The HA with the stoichiometric ratio 4: 1 were found in HF-formamide system. The results obtained were compared with the known data on the composition of HA formed in the binary liquid systems HF-DMF, HF-Me₂CO, and HF-MeCN. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1281–1287, July, 2007.     

Structural elucidation of hyaluronic acid gels after heat sterilisation

The influence of heat sterilisation and hyaluronic acid (HA) concentration on the micro- and macrostructure of HA hydrogels was investigated. HA hydrogels of different concentrations were prepared and heat sterilised. The microstructures of the polymer gels were characterised by positron annihilation lifetime spectroscopy (PALS) based on their ortho-positronium lifetime values and distributions, while their macrostructures were characterised by rheological measurements. As expected, the heat sterilisation modified both the micro- and macrostructures of the gels. The HA concentration was also observed to influence the hydrogel structure. At a concentration of 7.5 mg/ml HA, the thermal treatment did not cause significant microstructural changes, and the viscoelastic properties of the treated gels were similar to those of the untreated samples.