Collapse of polyelectrolyte networks induced by their interaction with an oppositely charged surfactant. Theory

A very simple theory of swelling and collapse of weakly charged polyelectrolyte networks in the solution of an oppositely charged surfactant has been developed. The following contributions to the free energy were taken into account: free energy of volume interaction and of elastic deformation of the network chains, free energy connected with micelle formation and free energy of translational motion of all mobile ions in the system (translational entropy). Both the cases of a solution of charged surfactant and that of a mixed solution of charged and neutral surfactant components have been taken into account. It has been shown that the behaviour of the network depends on the total surfactant concentration in the system and corresponds to one of the three following regimes: At low concentration, micelles inside the network are not formed and the behaviour of the polymer network is similar to that of a network swelling in the solution of a lowmolecular-weight salt (regime 1). In the second regime, surfactant concentration inside the network exceeds the critical micelle concentration and micelles are formed; in this regime the network collapses because surfactant molecules, aggregated in micelles, cease to create “exerting” osmotic pressure in the network sample. In the third regime, at very high surfactant concentration, formation of additional micelles inside the network ceases, and the network dimensions coincide with those of the corresponding neutral network.     

IPAAm凝胶在丙酮水溶液中溶胀行为的关联与预报

基于Maurer和Prausnitz的凝胶相平衡条件，建立了凝胶的溶胀模型.模型假设凝胶是以凝胶组分及凝胶吸收的溶液为核心，以弹性半渗透膜为壳的复合体.并采用UNIQUAC方程计算凝胶相及与之共存液相的Gibbs过剩自由能，采用“phantomnetwork”理论计算凝胶的弹性自由能，采用“自由体积”计算分子的尺度效应.同时以N-异丙基丙烯酰胺（IPAAm）为单体合成了IPAAm凝胶.研究了25 ℃时IPAAm凝胶在丙酮水溶液中的溶胀行为，并测定了丙酮在胶体相和与之共存液相中的分配，以检验模型的关联与预报能力.结果表明,模型预报的单体总量和交联剂浓度对凝胶溶胀的影响与实验符合得很好.而且凝胶溶胀时，能很好地预测丙酮在两相中的分配,表明模型具有很好的关联和预报能力.     

Understanding the elastomeric properties of polymer networks

It is shown that Monte‐Carlo (MC) simulations of the elastic behaviour of chains in networks using realistic rotational‐isomeric‐state (RIS) chain models are able to reproduce experimentally observed deviations from Gaussian network behaviour in uniaxial extension and also to interpret, quantitatively, stress‐optical properties. In stress‐strain behaviour, an increase in the proportion of fully extended chains with increasing macroscopic strain gives rise to a steady decrease in the rate of change of the Helmholtz energy of a network, causing a reduction in network modulus at moderate macroscopic strains. There is no need to invoke a transition from affine to phantom chain behaviour as deformation increases. To evaluate stress‐optical properties, the average orientation of segments with respect to the deformation axis is calculated, taking into account the interdependence of segment orientation and chain orientation as chains become more extended and aligned under uniaxial stress. The MC method gives, in agreement with experiment, values of stress‐optical coefficient that are dependent upon both deformation ratio and network‐chain length. The method highlights serious shortcomings in the classical Gaussian model of stress‐optical behaviour. Applications of the simulation methods to the quantitative modelling of the stress‐strain behaviour of poly(dimethyl siloxane) networks and the stress‐optical behaviour of polyethylene networks are described.     

New neutral and ionic poly(ethylene oxide) networks by radical polymerization

New opportunities resulting from a turn to radical polymerization in the synthesis of poly(ethylene oxide) (PEO) networks are discussed and exemplified. Several series of such networks have been prepared by radical homo‐ and copolymerization in aqueous media of “macromonomers”, i.e. partly methacrylated poly(ethylene glycol) (PEG) of varied molecular weight (MW ≅ 2000‐12000) and functionality (f_n ≅ 1.25‐1.8). This family of gels as a whole has the volume swelling degree Q in the range of 10 to 200 ml/ml. The hydrogels are characterized by means of Q, elastic modulus, swelling pressure, and with the use of some probes. The swelling behaviour of neutral hydrogels of this kind is briefly resumed. The multifunctional junctions formed in the propagation reaction of methacrylate end groups determine their main peculiarity. Anomalous elastic behaviour of the swollen networks prepared at high concentration of polymer has been observed and attributed to the network chains stretching of the same nature as in polymer stars or brushes. The junctions' functionality (F ≈ 20‐300) is evaluated from these data as well as from MW of the soluble models of network junctions. The PEO networks with charged units in junctions have been obtained by copolymerization of macromonomers with some ionic (meth)acrylic monomers. These gels display all the polyelectrolyte features, e.g. enhanced Q values in water (up to 50‐70) and, contrary to neutral PEO gels, the strong dependence on salt content. However, the osmotic contribution of mobile ions into swelling is shown to be low due to localization of charges in the junctions. The hydrogels that combine PEO and polymethacrylic acid chains capable of interpolymer complexation have been prepared and studied. They show much higher swelling in pure water (Q up to 200), strong deswelling by NaCl, and very sharp drop in swelling (ca. two order in Q) at pH ≈ 4.5‐5.5 due to complexation.     

辐射交联高聚物的溶涨与弹性性能的修正关系式

在辐射交联过程中,Charlesby假定交联度(及裂解度)与剂量成线性关系,导出了交联高聚物的溶涨与弹性性能关系式(1)及(2)。     

Preparation,optimization and swelling study of carboxymethyl sago starch (CMSS)–acid hydrogel

In this study, sago starch was modified in order to enhance its physicochemical properties. Carboxymethylation was used to introduce a carboxymethyl group into a starch compound. The carboxymethyl sago starch (CMSS) was used to prepare smart hydrogel by adding acetic acid into the CMSS powder as the crosslinking agent. The degree of substitution of the CMSS obtained was 0.6410. The optimization was based on the gel content and degree of swelling of the hydrogel. In this research, four parameters were studied in order to optimize the formation of CMSS–acid hydrogel. The parameters were; CMSS concentration, acetic acid concentration, reaction time and reaction temperature. From the data analyzed, 76.69% of optimum gel content was obtained with 33.77 g/g of degree of swelling. Other than that, the swelling properties of CMSS–acid hydrogel in different media such as salt solution, different pH of phosphate buffer saline solution as well as acidic and alkaline solution were also investigated. The results showed that the CMSS–acid hydrogel swelled in both alkaline and salt solution, while in acidic or low pH solution, it tended to shrink and deswell. The production of the hydrogel as a smart material offers a lot of auspicious benefits in the future especially related to swelling behaviour and properties of the hydrogel in different types of media.     

Group contribution method for the swelling behavior of thermo‐responsive hydrogels

A group contribution method is introduced to describe the swelling behavior of thermo‐sensitive hydrogel systems. The accuracy of group contribution calculations is strongly dependent on the choice of thermodynamic model. Therefore, we revise the modified double lattice (MDL) model and develop a new expression for the interaction energy parameter using the association theory of Sanchez to take into account complex polymer/solvent mixing. The net Helmholtz energy for a hydrogel is established by combining the revised MDL model and modified Flory–Rehner elastic model. Group parameters are generated by fitting to experimental swelling data from both homopolymer and copolymer gel systems. The effect of salt on the volume phase transition is modeled by introducing an additional salt‐specific parameter to investigate various stimuli‐response swelling behavior. Calculated swelling equilibria using the new group contribution method shows excellent agreement with experimental data and various stimuli‐response volume phase transitions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 455–463     

Polyampholyte gels: swelling,collapse and interaction with ionic surfactants

Two series of polyampholyte gels formed from sodium methacrylate and diallyldimethylammonium chloride with variable composition were synthesized in water and in aqueous salt solution. It is shown that the swelling properties of polyampholyte gels are directly related to their chemical structure, which is defined by the process of gel synthesis. The swelling ratio of the polyampholyte gels prepared in salt solution is large compared with the gels prepared in pure water i.e. the polyampholyte gels with balanced stoichiometry show minimal swelling.The interaction of the polyampholyte gels with ionic surfactants (cationic, cetylpyridinium chloride and anionic, sodium dodecylbenzenesulphonate) was studied. It was shown that for polyampholyte gels with an excess of the charges of one sign the addition of oppositely charged surfactant leads to the collapse of the gel. It was found that the efficiency of surfactants absorption is determined by the ratio of positive and negative charges in the chains of polyampholyte gels.     

一种温敏萃取凝胶

本工作合成了一种温敏萃取凝胶,即N-异丙基丙烯酰胺与甲基丙烯酸钠的共聚物凝胶。分别考察了在合成凝胶时,离子剂用量和交联剂用量对凝胶溶胀性能的影响。还考察了在不同溶剂中和在酸、碱、盐存在下凝胶的溶胀情况,以及凝胶的再生性能。此种新温敏凝胶,于室温下在水中的溶胀比明显高于文献中报道的其他温敏凝胶,而且其再生性能良好,在水中溶胀皱缩反复到第10次时,其吸水性能无什么变化。     

Concentration polydispersity in polymer gels

For swollen polymer networks there is no generally accepted relation between the macroscopic osmotic properties and the scattering behaviour. Detailed information on the relationship between these properties can, however, be deduced from complementary measurements of osmotic and elastic behaviour, small angle neutron and X-ray scattering (SANS and SAXS) and quasi-elastic light scattering. We describe such an investigation in two types of networks, differing in the mechanism of cross-linking. The SANS spectra yield information on the structure, which is generated both by the dynamics of the system and by long range static constraints. The former, arising from thermodynamic concentration fluctuations, governs the macroscopic osmotic and elastic moduli of the swollen network. The static superstructure in the gel reflects local variations in the cross-link density. The resulting concentration polydispersity, <δφ²>/φ², is determined by the details of the cross-linking procedure. Its concentration dependence as a function of gel swelling can be expressed in terms of the same macroscopic osmotic and elastic variables as those that govern the thermodynamic properties of the gel.     

A general gel layer model for the transport of colloids and macroions in dilute solution

A general boundary element methodology for studying the dilute solution transport of rigid macroions that contain gel layers on their outer surfaces is developed and applied to several model systems. The methodology can be applied to particles of arbitrary size, shape, charge distribution, and gel layer geometry. Account is also taken of the steady state distortion of the ion atmosphere from equilibrium, which makes it applicable to the transport of highly charged structures. The coupled field equations (Poisson, ion-transport, low-Reynolds-number Navier-Stokes, and Brinkman) are solved numerically and from this, transport properties (diffusion constants, electrophoretic mobilities, excess viscosities) can be computed. In the present work, the methodology is first applied to a gel sphere model over a wide range of particle charge and the resulting transport properties are found to be in excellent agreement with independent theory under those conditions where independent theory is available. It is then applied to several prolate spheroidal models of a particular silica sol sample in an attempt to identify possible solution structures. A single model, that is able to account simultaneously for all of the transport behavior, which does not undergo significant conformational change with salt concentration, could not be found. A model with a thin (相似文献   

SYNTHESIS AND CHARACTERIZATION OF AMPHOTERIC HYDROGELS BASED ON N-CARBOXYETHYLCHITOSAN

New amphoteric hydrogels based on carboxyethylchitosans(CECH)with various degrees of substitution(DS) were prepared using different amounts of epichlorohydrin(ECH)as the crosslinking agent.The equilibrium swelling ratio (SW)was determined as functions of pH and salt concentration.The hydrogels show typical amphoteric character responding to pH change of the external medium.At isoelectric point(IEP),the hydrogels shrink.The DS value has important effect on the swelling properties of the hydrogels.When the...     

Swelling,elasticity and structure of hydrogels prepared via bis-macromonomers of poly(ethylene oxide)

The effect of swelling on the shear modulus was studied for hydrogels prepared by radical polymerization of methacrylate-terminated poly(ethylene oxide) (PEO) bis-macromonomers of different molecular weight. Gels made of long chains (M = 12000 or 6000) display classical softening upon swelling, whereas gels made of shorter chains (M = 4000 or 2000) remain rigid or even stiffen. The abnormal behaviour is explained by a specific character of network junctions presented by polymethacrylate chains in which each unit is linked with a PEO network chain. It is assumed that the interactions among densely grafted PEO chains result in their stretching on polymerization and non-affine deformation on swelling, which stiffen the gel. This is verified by the data on copolymer (macromonomers - 2-hydroxyethyl methacrylate) gels that have lesser densities of PEO chains attached to the junctions and show weaker stiffening on swelling. The osmotic pressure of gels was estimated from the swelling pressure and shear modulus. Similar to the mixing pressure of equivalent PEO solutions, it varies as the 9/4 power of polymer concentration. At the same time, it is lower than the mixing pressure. This indicates that the junctions make only quantitative changes in the osmotic properties of macromonomer chains.     

Solvent-based nanocomposite coatings I. Dispersion of organophilic montmorillonite in organic solvents

This study aims to determine the relevant parameters controlling the organophilic montmorillonite dispersion in various organic solvents which can be used as dispersion media for polymer coatings. These suspensions were studied at three scales: At nanometer scale by looking to interlayer distance: When the solvent surface energy is higher than the organophilic clay surface energy, i.e., gamma solvent > or = gamma montmorillonite, the intercalated organic chains of the quaternary ammonium modifier swell, leading to an increase of the interlayer distance. The balance between hydrophilic and hydrophobic character is the key to dispersion of nanoclays. At micrometer scale by studying the rheological behaviour of clay suspensions: Gels are formed by percolation of microgels, based on swollen 3-4 platelet tactoids. The viscoelastic properties and the flow behavior reveal the gel structuration by measuring the gel stiffness and the flowing stress. At macroscopic scale analyzed from the swelling of the nanoclay into solvents: The compatibility between solvent and organophilic clay governs the macroscopic swelling, i.e., interactions between organic chains borne by the intercalated ions and solvents govern the final suspension morphologies. The same methodology can be adopted for monomers or prepolymers selected for one in situ intercalation/exfoliation processing route.     

Tricritical point induced by smectic ordering of a nematic gel

The authors study volume phase transitions of a nematic gel immersed in a liquid crystal (LC) solvent, which shows a second-order nematic-smectic A phase transition (NST). Combining Flory's elastic energy [Principles of Polymer Chemistry (Cornell University Press, Ithaca, 1953)] for a swelling of the gel with the McMillan model [Phys. Rev. A 4, 1238 (1971)] for smectic ordering, the authors calculate the equilibrium swelling of the gel and smectic order parameters as a function of temperature. The authors take into account an attractive interaction parameter c between the gel and LC solvents. On increasing the value of the coupling constant c, a second-order NST of the gel is changed to a first-order one and a continuous volume phase transition of the gel is changed to a discontinuous one. The authors find a tricritical point of the gel induced by smectic ordering.     

Thermodynamic Equilibrium between an Ionite's Gel Part and a Simple-Salt Solution with Allowance for Water Dissociation

When solving an ion-exchange equilibrium problem it is usually taken into account that the ionite, according to a two-phased model, comprises microphases of a gel and an equilibrium solution. The question of equilibrium in this case involves the necessity to take into account not only ions of salt contained in an aqueous solution, but ions of hydrogen and hydroxyl, which emerge in the water dissociation process, as well. Setting up such a problem is dictated, for example, by the application of electrodialysis for the production of deeply-desalinated water. In the work, for a solution of a simple salt, relations are established, which allow one to compute complete ionic composition of phases of solution and gel on the basis of specified values of concentrations of cations and anions of salt in solution.     

Large deformation rheology of gelatin gels

We studied the linear and the non-linear elastic behaviour, the breaking stress and breaking strain of gelatin gels as a function of a number of experimental conditions: gelatin concentration, gelatin bloom value, ageing time, ageing temperature, pH, NaCl and CaCl₂ concentration, whey protein concentration, the amount of pre-shearing, strain rate or compression speed, using both shear deformation and compression. We analyzed the stress-strain curves using the BST-equation (Blatz et al., Trans. Soc. Rheol. 18, (1974) 145) and extracted a parameter that characterizes the linear elastic behaviour at small deformations (the moduli E or G) and one that characterizes the non-linear elastic behaviour at large deformations (the elasticity parameter n). The phenomenological BST equation describes rheological experiments adequately both in shear deformation and in compression.We found that the modulus correlates with the breaking stress. For the non-linear elastic properties of gelatin, we found that the elasticity parameter n correlates with the breaking strain Qualitatively, the non-linear elastic properties can be explained by assuming that the gelatin chains are partially in a crystalline triple helix state (the cross-links) and partially in a random coil state (the network bonds): the more extensive the rigid cross-link regions, the shorter and more stretched the network bonds become as a result of an externally applied deformation. The network bonds behave as anharmonic springs under extreme extension.Manipulation of the breaking strain was attempted in two ways: (i) by changing the (non-linear) elasticity parameter of the gel: this is possible by using a gel that has been further aged; (ii) by adding defects to the gel structure: this is possible by either pre-shearing the gel or by adding whey protein particles. The pre-shearing gives rise to a temporary effect, the addition of whey protein particles to a permanent effect.     

Rheological study of transient networks with junctions of limited multiplicity

We theoretically study the viscoelastic and thermodynamic properties of transient gels comprised of telechelic associating polymers. We extend classical theories of transient networks so that correlations among polymer chains through the network junctions are taken into account. This extension enables us to investigate how rheological quantities such as elastic modulus, viscosity, and relaxation time are affected by the association equilibrium, and how these quantities are related to the aggregation number (or multiplicity) of the junctions. In this paper, we assume, in the conventional manner, that chains are elastically effective if both their ends are connected with other chains. It is shown that the dynamic shear moduli are well described in terms of the Maxwell model. As a result of the correlation, the reduced moduli (moduli divided by the polymer concentration) increase with the concentration, but become independent of the concentration in the high-concentration range. The fraction of pairwise junctions is larger at lower concentrations, indicating the presence of concatenated chains in the system, which decreases as the concentration increases. This leads to a network relaxation time that increases with the concentration.     

The colloidal behaviour of kraft lignin III. Swelling behaviour and mechanical properties of kraft lignin gels

Summary Kraft lignin gels have been synthesized by cross-linking kraft lignin (Indulin ATR) in water with varying amounts of epichlorohydrin under alkaline conditions. The effects of pH and salt concentration on the swelling behaviour and on the mechanical properties of these gels have been investigated.Swelling was determined gravimetrically and the mechanical properties of the gels were tested under uni-axial compressive creep in the time interval 1–900 s. The gels show a linear viscoelastic behaviour without viscous flow.The kraft lignin gels exhibit a swelling behaviour typical for polyelectrolytic networks, i. e. the degree of swelling increases with an increasing number of ionized groups and decreases with increasing salt concentration. The swelling behaviour and ion exchange capacity were found to be nonspecific towards type of alkaline solution (LiOH, NaOH, and KOH).The ability of the carboxylic groups to form intermolecular hydrogen bonds has a strong influence on the mechanical properties of the gels. Creep compliance and creep rate increase greatly when the carboxyl groups are dissociated. It is therefore concluded that the effective number of crosslinks in the networks in addition to chemical cross-linking is also dependent on the state of dissociation of the carboxylic groups.With 11 figures and 1 table     

On possible microscopic origins of the swelling of neutral lipid bilayers induced by simple salts

It was recently suggested that the swelling of neutral multilipid bilayers upon addition of a salt can be simply explained only by the electrolyte screening of the van der Waals attractions, while assuming that the hydration force and the repulsion due to thermal undulations of membranes are unaffected by the salt. While we agree that the screening of the van der Waals interactions plays a role, we suggest that the increase in the hydration force upon addition of a salt has also to be taken into account. In a statistical model, which accounts for the membrane undulations, parameters could be found to explain the multibilayer swelling even when the van der Waals attraction is considered unaffected by the electrolyte screening. These results point out that the decrease by a factor of three of the Hamaker constant upon addition of a salt, suggested recently to be responsible for the swelling of neutral multilipid bilayers, is perhaps too large, and a smaller decrease in Hamaker constant, coupled with the above mentioned effects might explain the swelling.