Neutron scattering in polymer gels at the theta temperature

Small angle elastic neutron scattering was performed on three polystyrene networks swollen to equilibrium in cyclohexane at the theta temperature. Comparison of the SANS spectra with similar measurements in uncross-linked solutions reveals that in the intermediate Q region the gels behave like solutions of lower concentration than the equivalent solutions. We assume that the gel spectra are composed of a static component plus a dynamic, or solution-like part. By a suitable fitting procedure, the former can be estimated, yielding the mean square static concentration fluctuation <Δφ²> generated by cross-linking contraints in the gel. Independent measurement of the swelling pressure of these gels permits an estimate to be made of the scattering intensity I(Q=0) of the dynamic part of the spectrum. Plausible agreement is found between the macroscopic and microscopic estimations of the osmotic compressibility if allowance is made for the concentration polydispersity in the gels.     

Calcium induced volume transition in polyelectrolyte gels

The osmotic properties and the small angle neutron scattering (SANS) behaviour of fully neutralized sodium polyacrylate gels are investigated in the presence of calcium ions. Analysis of the SANS response displays three characteristic length scales, two of which are of thermodynamic origin, while the third, associated with the frozen-in structural inhomogeneities, is static. The SANS results are consistent with direct osmotic observations which indicate that the thermodynamic properties cannot be adequately described by a single correlation length. The concentration dependence of the osmotic pressure displays a power law behaviour with an exponent that decreases with increasing calcium concentration.     

Quasi-elastic neutron scattering in gels and solutions

Measurements of swelling pressure, neutron spin-echo scattering, and dynamic light scattering were made in an end-linked poly(dimethylsiloxane) (PDMS) gel swollen to equilibrium in a good solvent (toluene) and also in the equivalent solution. The macroscopic osmotic modulus is depressed in the gel. Neutron spin echo observations at intermediate and high values of the scattering vector Q reveal that the mobility of the monomers is unaffected by cross-linking. Elastic neutron scattering at small Q detects non-uniformities in the polymer concentration distribution, which are absent from the solution. These non-uniformities play a major role in the dynamic response of the system at lower Q, and and appear to be the cause of the observed reduction in osmotic pressure.     

Molecular aspects of polymer network deformation - small angle neutron scattering and NMR studies

Poly(1,4-butadiene) networks obtained by a 4-functional random cross-linking reaction over a broad range of polymer concentration were studied by small angle neutron scattering(SANS), ²H NMR and Monte Carlo(MC) simulation in the isotropic and uniaxially deformed state. The defect structure of the networks has been characterized by MC simulation of the cross-linking reaction. The anisotropy of the radius of gyration in deformed networks determined from SANS has been analyzed by the theory of Ullman. It was found that the number of active cross-links per chain is in agreement with MC and that the chain deformation follows phantom behaviour. The local orientation as measured by ²H NMR is related to the global anisotropy of the network by a MC calculation of oriented chains. The ²H NMR line shape of the deformed network is analyzed in terms of two relaxation processes arising from interior parts of the chains and from segments at chain ends. The mobility of both decrease with strain. It was found that the orientation connected to the first process shows the classical strain dependence of rubber elasticity, whereas the second exhibits a weaker dependence on strain.     

Characterization of inhomogeneous polyacrylamide hydrogels

The physical and structural properties of acrylamide gels have been characterized by osmotic deswelling, mechanical compression, and x-ray scattering. These properties vary considerably with the concentration of the crosslinking agent bisacrylamide, at fixed total monomers concentration (10% wt/wt water). In particular, changes in the properties appear more prominent at a crosslinking level of about 5-6% (wt bisacrylamide/wt monomers). The compression modulus of as-prepared and swollen gels passes through a maximum at this level of crosslinking. The swelling pressure curves can be separated into osmotic and elastic contributions of the gel network. The elastic part exhibits similar behavior to the compression modulus. The scaling of the osmotic part with the gel concentration varies with the degree of crosslinking, changing from 2.33 to 3.09. This indicates that the solvent power of water decreases with increasing crosslinking level, towards Φ conditions. The scattering patterns from the gels have been analyzed as arising from additive contributions from a homogeneous gel matrix, and embedded heterogeneities having a higher crosslinking density. These heterogeneities become much more prominent at the same level of crosslinking about 5-6%. Hysteresis observed in the sorption/desorption behavior of polyacrylamide gel suggests that further irreversible structural changes may occur at water activities lower than probed by osmotic deswelling. © 1992 John Wiley & Sons, Inc.     

Continuous swelling pressure equilibria of the systemκ-carrageenan/water

The deformation of -carrageenan/water gels in a centrifugal field leading to a continuous equilibrium is described. These gels form three-dimensional physical networks. The concentration gradient and the movement of the meniscus gel/solvent during the change of the concentration in the gel phase is measured with a Schlieren optical system of an analytical ultracentrifuge. The gel is considered to be a binary elastic mixture of crosslinked polymer and solvent and is assumed to remain isotropic during the deformation. The concentration dependence of the swelling pressure in the concentration range between the maximum swollen gel and that at the cell bottom can be obtained in a single equilibrium experiment. For the avaluation of the experiments, the weight fraction of the polymer in the maximum swollen gel has been determined separately by a gravimetric method.By means of the swelling pressure-concentration curves the thermodynamic properties of the investigated -carrageenan/water gels can be calculated. The system can be described semi-empirically with a slightly modified Flory-Huggins equation with an interaction parameter _w in the weight fraction scale, which depends linearly on the concentration. The dependence of the static shear modulusG on the polymer concentration follows the scalling theory of De Gennes.Dedicated to Prof. Dr. Ronald Koningsveld on the occasion of his 70th birthday     

Swelling and scattering investigations on chemically cross-linked poly(vinyl alcohol) hydrogels

Swelling and scattering measurements are reported from chemically cross-linked polyvinyl alcohol) hydrogels and the corresponding semi-dilute polymer solutions. The mixing free energy in the swollen network is found to be significantly smaller than that of the corresponding polymer solution at identical concentration. Static light scattering and small-angle neutron scattering measurements indicate the presence of large-scale static structures in the solution. Reasonable agreement is found between the osmotic moduli obtained from light scattering measurements and macroscopic osmotic observations.     

Micro- and mesoscopic structure of poly(vinyl alcohol) gels determined by neutron and light scattering

We studied the structure of poly(vinyl alcohol) (PVA) gels formed in mixtures of dimethyl sulfoxide (DMSO) and water using several scattering techniques such as wide-angle neutron scattering (WANS), small-angle neutron scattering (SANS), ultra-small-angle neutron scattering (U-SANS) and light scattering (LS) to cover a very wide Q range from 10^-4 to 10 Å^-1. The WANS measurements have revealed that the cross-linking points of the gels are crystallites, and the size and its distribution have been evaluated by the SANS measurements. The SANS results have also shown that the structure observed in the low Q range below 10^-2 Å^-1 is dominated by a liquid–liquid-phase separation. The early stage of the phase separation has been studied in detail using the time-resolved LS technique, while the late stage has been investigated by the U-SANS technique because the LS measurements cannot access the opaque samples. On the basis of the results, we present a quantitative sketch of the structure of the PVA gel.     

Ringing gels: Their structure and macroscopic properties

The phase diagram of the ternary surfactant system which consists of dimethyltetradecylaminoxide, hydrocarbon, and water contains a highly elastic gel phase which borders on the micellarL ₁-phase. This gel phase is transparent, optically isotropic, and shows the ringing phenomena when it is excited to mechanical vibrations. From SANS and light-scattering measurements it is shown that this phase consists of the same spherical microemulsion droplets which are present in the adjacent micellar solution. Even in the micellar solution the droplets are fairly monodisperse and in the SANS scattering functions a second scattering maximum was observed. Both the light scattering and SANS data can be described quantitatively on the basis of hard sphere interactions between the particles. Furthermore, it is shown that elasticity and shear modulus of the gel phase, which were determined experimentally, correlate with the compressibility modulus as calculated from the scattering data. The elasticity modulus and hence the osmotic compressibility modulus are related to the Laplace pressure inside the globules. For the calculation of this pressure it is possible to take the interfacial tension, which is obtained from a dilute micellar solution against the hydrocarbon which is used for the system. The radius of the particles and the hydrocarbon content in the system can be increased when some of the dimethyltetradecylaminoxide is replaced by dimethyltetradecylphosphinoxide.     

Thermodynamic interaction parameters in polymer solutions and gels

Polymer-solvent interaction parameters are reported for poly(vinyl acetate)-acetone, poly(vinyl acetate)-toluene, and poly(dimethyl siloxane)-toluene systems using different techniques. Results obtained by osmotic deswelling are compared with those from quasi-elastic light scattering and small-angle neutron scattering (SANS). In gels, the latter techniques involve separation of the time-dependent from the static component of the scattered radiation+ Separation is achieved in quasi-elastic light scattering through the heterodyning properties of the light, and in SANS by subtracting an appropriate static structure factor. The interaction parameters obtained by different separation procedures are consistent with measurements using the osmotic method. © 1995 John Wiley & Sons, Inc.     

Concentration fluctuations in polymer gel investigated by neutron scattering: static inhomogeneity in swollen gel

By using small-angle neutron scattering (SANS) and neutron spin echo (NSE), we have quantitatively investigated the static inhomogeneity in poly (N-isopropyl acrylamide) gel (PNIPA) in microscopic length scales of 0.015相似文献   

Small-angle neutron scattering study on microstructure of poly(N-isopropylacrylamide)-block-poly(ethylene glycol) in water

By employing small-angle neutron scattering (SANS), we investigated the microstructures of, poly(N-isopropylacrylamide) (PNIPA)-block-poly(ethylene glycol) (PEG) (NE) in deuterated water D₂O, as related to macroscopic behaviors of fluidity, turbidity and synerisis. SANS revealed following results: (i) microphase separation occurs at around above 17 °C in a temperature range of transparent sol below 30 °C. In the microdomain appeared in the transparent sol state, both block chains of PNIPA and PEG are swollen by water; (ii) for the NE solution of polymer concentration W_p > 3.5% (w/v), corresponding to opaque gel above 30 °C, a percolated structure, i.e., network-like domain is formed by NE as a result of macrophase separation due to dehydration of the PNIPA chains. As the temperature increases toward 40 °C, the network domain is squeezed along a direction parallel to the NE interface, which leads to increase of the interfacial thickness given by swollen PEG chains and to the macroscopic synerisis behavior.     

Structural and dynamic single chain behaviour in a binary blend of low molecular mass poly(siloxanes) as studied by small angle neutron scattering and neutron spin echo spectroscopy

Elastic and quasi elastic neutron scattering investigations, using the small angle neutron scattering (SANS) and neutron spin echo (NSE) techniques, respectively, were performed in order to study the static and dynamic single chain behaviour in a binary blend of low molecular mass deuterated poly(dimethylsiloxane) (d-PDMS) and protonated poly(ethylmethylsiloxane) (p-PEMS) at the critical composition _c. Since the single chain observation requires that only a small amount of one of both components is labelled, the d-PDMS/p-PEMS system was modified in such a way that the major part of the protonated PEMS component was replaced by the corresponding deuterated material. Although the de-mixing of the PEMS isotopes occurs far below the de-mixing of the PDMS/PEMS system the resulting chemically binary d-PDMS/d-PEMS/p-PEMS blend with the volume composition 0.5/0.425/0.075 is strictly speaking a ternary system. This complication had to be taken into account, in particular with respect to the correct evaluation of the SANS data.The careful analysis of the SANS curves allows one to determine all three thermodynamic interaction parameters with reasonable reliability and gives evidence that the radii of gyration agree with those, which were determined in corresponding isotopic PDMS and PEMS blends. This is in contrast to the observation on real binary PDMS/PEMS blends at _c, where the collective conformational properties exhibit a considerable chain expansion. The NSE data of the ternary system follow completely the predictions of the Rouse model, which describes the dynamics of a dense low molecular mass polymeric system in a single chain approximation. The experimental observations are also in contrast to the results of former NSE measurements on binary PDMS/PEMS blends, where a transition from Rouse behaviour at short times to a much weaker relaxation at longer times became obvious.The results of the static and dynamic single chain behaviour presented here confirm the results of a computer simulation on a low molecular mass binary blend at the critical concentration, where explicitly the pure single chain behaviour was probed and no indications for chain expansion and deviations from the Rouse dynamics were found.Dedicated to Prof. Dr. Erhard W. Fischer on the occasion of the 75th anniversary of his birthday.     

Neutron scattering and swelling properties of end-linked polydimethylsiloxane networks

Small angle neutron scattering measurements were performed on polydimethylsiloxane-toluene solutions and gels at different degrees of swelling. The scattering signal of the gel was decomposed into a solution-like part and a static part. The thermodynamic information obtained from the solution-like part of the signal is compared with macroscopic swelling pressure observations.     

Rheological and structural properties of aqueous solutions of a hydrophobically modified polyelectrolyte and its unmodified analogue

Rheological methods and small angle neutron scattering (SANS) were used in the characterization of dilute and semidilute aqueous solutions, both with and without added salt, of anionic poly(vinyl alcohol) (PVA⁻) and its hydrophobically modified analogue (HM-PVA⁻). The rheological measurements showed that the concentration induced viscosification effect and elastic responses are considerably stronger for solutions of HM-PVA⁻ than in solutions of the unmodified polyelectrolyte. Over the considered polymer concentration domain, the solutions of PVA⁻ exhibit virtually Newtonian behavior, whereas strong shear thinning effects are observed in the HM-PVA⁻ solutions. The SANS results for HM-PVA⁻ solutions reveal a pronounced peak in the plot of scattering intensity versus scattering wavevector q at intermediate q values and the position of the maximum scales with polymer concentration as q_max∼c^0.28±0.02. This peak is suppressed in solutions of the unmodified polyelectrolyte and merely a shoulder in the scattering curve appears. Additionally, an “upturn” in the scattered intensity is observed at small q values and the magnitude of this effect depends on polymer concentration, hydrophobicity and salt addition. At large q values, the SANS results from HM-PVA⁻ solutions suggest morphological changes, from rod-like chains to a network of semiflexible chains, as the polyelectrolyte concentration increases.     

3D Networks from Self-Assembling Ionic-Complementary Octa-Peptides

The self-assembly and gelation properties of a set of four octo-peptides AEAEAKAK, AEAKAEAK, FEFEFKFK and FEFKFEFK based on alanine (A), phenylalanine (F), lysine (K) and glutamic acid (E) were investigated via small angle neutron scattering (SANS). The SANS experiments suggest that AEAKAEAK peptide does not self-assemble in solution while AEAEAKAK form rod-like structure i.e.: fibres with a radius of ∼3.3 nm. The latter peptide does not form a gel suggesting that the fibres do not aggregate and form a three-dimensional network. On the other hand FEFEFKFK and FEFKFEFK peptides were found to form gels for concentrations higher than ∼7 mg ml⁻¹. Below the critical gelation concentration these peptides were also found to form fibrillar structures with smaller average radii of ∼1.7 nm. Above the critical gelation concentration a scattering maximum is observed in the scattered intensity curve. From the position of the maximum a rough estimation of the mesh size of the gel network could be derived and was found to vary between 15 and 30 nm depending on the gel concentration.     

Volume transition and internal structures of small poly(N‐isopropylacrylamide) microgels

Monodispersed poly(N‐isopropylacrylamide) (PNIPAM) nanoparticles, with hydrodynamic radius less than 50 nm at room temperature, have been synthesized in the presence of a large amount of emulsifiers. These microgel particles undergo a swollen–collapsed volume transition in an aqueous solution when the temperature is raised to around 34 °C. The volume transition and structure changes of the microgel particles as a function of temperature are probed using laser light scattering and small angle neutron scattering (SANS) with the objective of determining the small particle internal structure and particle–particle interactions. Apart from random fluctuations in the crosslinker density below the transition temperature, we find that, within the resolution of the experiments, these particles have a uniform radial crosslinker density on either side of the transition temperature. This result is in contrast to previous reports on the heterogeneous structures of larger PNIPAM microgel particles, but in good agreement with recent reports based on computer simulations of smaller microgels. The particle interactions change across the transition temperature. At temperatures below the transition, the interactions are described by a repulsive interaction far larger than that expected for a hard sphere contact potential. Above the volume transition temperature, the potential is best described by a small, attractive interaction. Comparison of the osmotic second virial coefficient from static laser light scattering at low concentrations with similar values determined from SANS at 250‐time greater concentration suggests a strong concentration dependence of the interaction potential. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 849–860, 2005     

Cooperative diffusion in partially neutralized poly(acrylic acid) gels

Poly(acrylic acid) networks swollen with water and having different ionization degrees and different polymer concentrations, were investigated using elastic and quasi-elastic light scattering. The scattered intensity was found to vary as the ratio of the polymer concentration to the ionization degree, which shows that the osmotic pressure is dominated by counterion entropy. The behavior of the cooperative diffusion coefficient cannot be explained by the scaling theories and involves an unexpected variation of the frictional coefficient with polymer concentration.     

Light,Small Angle Neutron and X-Ray Scattering from Gels

This paper gives two examples of experiments that demonstrate the power of small angle scattering techniques in the study of swollen polymer networks. First, it is shown how the partly ergodic character of these systems is directly detected by neutron spin echo experiments. The observed total field correlation function of the intensity scattered from a neutral gel allows the ergodic contribution to be directly distinguished from the non ergodic part, at values of transfer wave vector q that lie well beyond the range of dynamic light scattering. The results can be compared with those obtained at much lower q from visible light scattering. Second, a recent application of small angle X-ray (SAXS) and neutron (SANS) scattering is described for a polyelectrolyte molecule, DNA, in semi-dilute solutions under near-physiological conditions. For these observations, the divalent ion normally present, calcium, is replaced by an equivalent ion, strontium. The comparison between SANS and SAXS yields a quantitative picture of the cloud of divalent counter-ions around the central DNA core. At physiological conditions, the cloud is thinner than that predicted on the basis of the Debye screening length but thicker than if the counter-ions were condensed on the DNA chain.     

A novel orientation technique for semi-rigid polymers. 1. Preparation of cross-linked cellulose acetate and hydroxypropylcellulose films having permanent anisotropy in the swollen state

It has been predicted that unusually good mechanical properties can be obtained by drying swollen networks of semi-rigid chains while they are in the deformed state, as described in several theoretical investigations [Macromolecules,23: 5335, 5341 (1990),24: 901 (1991)]. The present investigation involves the preparation of networks of this type from cellulose acetate (CA) and hydroxypropylcellulose (HPC), in order to test these concepts. The cross-linking required to maintain anisotropy during the drying process was obtained using formaldehyde, while the polymers were in either the anisotropic or isotropic state. Control of the cross-linking was obtained by studying the effects of the concentration of formaldehyde, temperature, and reaction time.The liquid-crystalline phase separations in CA and HPC, and in their networks, were studied with cross-polarized optical microscopy. CA and HPC showed anisotropic phases in trifluoroethanol and in methanol, respectively, and under shear the HPC systems exhibited the band textures associated with macroscopic orientation. In the case of the uncross-linked polymers, this band texture disappeared shortly after shearing was discontinued. The networks prepared by cross-linking the HPC in either liquid-crystalline solutions or in isotropic solutions also showed band textures, but these textures now persisted long after removal of the shearing stress. As shown in the following paper, the extensibility required in the proposed processing technique was highest for the networks prepared in the isotropic state, suggesting that these materials should have the greatest potential for dramatic improvements in mechanical properties.