Initial density fluctuations effects on the microphase separation in ramified polymer mixture

Our study focuses on the initial density fluctuations effects on microphase separation in ramified polymer mixture. For this purpose, we introduce a screening length κ   by considering the condition that the scattered intensity should not be changed by cross-linking. We recover that κ²∼C/(χ−χi)${\kappa }^2\sim C/(\chi -{\chi }_i)$, where C is the rigidity constant of the network and χ the Flory parameter. Three regimes versus the temperature of the mixture are discussed. The kinetics of the microphase separation is also studied through the relaxation rate. The derived relaxation rate evolution relative to ramified polymers mixture must be compared to that relative to a linear polymer mixture. Finally, we discuss the solvent effect on the microphase separation and we show that the initial fluctuations have little importance because of the excluded volume interaction.     

Kinetics of microphase separation in interpenetrated polymer networks in solution

We present here a theoretical study of the early kinetics of the microphase separation in crosslinked polymer blends, made of two incompatible polymers A and B, dissolved in a common good solvent. Use is made of an extended blob model used previously for the investigation of the static properties of such a transition. We are interested in the variation of the relaxation rate, , versus the wave number q, in the vicinity of the spinodal temperature. We first show that kinetics is entirely dominated by local motions, which are of Rouse type. Slow motions are absent, because of the permanent presence of crosslinks. Second, we find that the characteristic frequency, (q ) = , increases with increasing wave number q according to a sixth power law, that is (q ) q^6{-9/4}, where is the overall monomer volume fraction. Therefore, the swelling of strands due to the excluded-volume forces leads to a renormalization of the characteristic frequency by a multiplicative factor scaling as ^{-9/4}. The main conclusion is that the presence of a good solvent necessitates relaxation rates less important than those relative to crosslinked mixtures in the molten state.     

Extension of integral equation theory to microphase separation of block copolymers

The confined polymer reference interaction site model (Wall-PRISM) integral equation theory was applied to investigate the microphase separation behaviour of copolymers at a solid surface or in bulk. In particular, the effects of the solid surface on polymer conformation were taken into account for constructing a set of novel bridge functionals for different segments to improve the theory. After the integration of the bridge functionals, the theory can well reproduce the simulated density profiles at different microphase domains of flexible–flexible, flexible–rigid, and linear–branched copolymers. As a consequence, the application scope of the inhomogeneous theoretical approach has been extensively extended. This work provides a prospective way to quantitatively predict the density profiles in microphase separation for block copolymers with sophisticated conformation.     

Determination of pore space shape and size in porous systems using NMR diffusometry. Beyond the short gradient pulse approximation

The influence of finite length gradient pulses on NMR diffusion experiments on liquids confined to diffuse between two parallel planes is investigated. It is experimentally verified that the pore size decreases when determined using finite gradient pulses if the results are analyzed within the short gradient pulse approximation. The results are analyzed using the matrix formulation. The observed minima in the echo decay profiles are considerably less sharp than theoretical analysis would indicate and we suggest that this is due to the presence of a distribution of pore sizes in the sample. In addition, effects due to the presence of background gradients are discussed. It is argued that effects due to the finite length gradient pulses are relatively minor and in realistic applications the effects due to inhomogeneities in pore sizes and effects due to background gradients will constitute more serious problems in pore size determinations by means of NMR diffusometry.     

氟锆酸盐光纤玻璃中的析晶和分相现象

氟化物光纤玻璃中的夹杂物,分相颗粒和微晶颗粒等缺陷,造成光纤的散射损失,影响了实际制备工作.本文利用大视场光学显微镜,X射线衍射,透射电子显微镜和差热分析,研究了ZBLA氟化物玻璃中的分相和析晶现象,观察到了以成核生长机理进行的分相颗粒,析晶颗粒的成分是β-BaF_2·ZrF_4和α-BaF_2·2ZrF_4,通过DTA分析确定了这些相的析晶活化能.     

Curie temperature and frustrated phase separation in manganites

There is an increasing experimental evidence that phase separation between insulating and metallic phase plays an important role in the physics of manganites. On general grounds one can argue that the electronic density in the metallic and insulating region will be generally different. This implies that phase separation of the ordinary “Maxwell construction” type is frustrated by the long-range Coulomb interaction. We present a generalization of Maxwell construction to this situation. The system is assumed to separate in islands of one phases hosted by the other. The size of the islands is determined minimizing a free energy that takes into account both surface energy and Coulomb effects. We discuss the peculiarities of this kind of phase separation and the consequences for the manganites. In particular, we present an explanation for the non-monotonous behavior of the Curie temperature as a function of doping.     

Microphase separation in polydisperse miktoarm star copolymers

A two or more chemically different homopolymers attached to a single junction point form a macromolecule of miktoarm star copolymer. The model of such copolymer composed of an arbitrary number of types of homopolymer arms is considered. The lengths distributions of arms are assumed to be arbitrary, provided that average length of an each arm is long enough. The algorithm is suggested to find the contributions into the Landau free energy of this copolymer melt which are necessary to obtain a phase diagram in weak segregation regime. Using this algorithm the contributions are found up to the fourth order. The phase diagrams have been constructed for the simple model of AB₂ copolymer melt whose macromolecules consist of polydisperse A-block and two monodisperse B-blocks.     

Phase separation, percolation and giant isotope effect in manganites

Phase separation and a tendency to form inhomogeneous structures seems to be a generic property of systems with strongly correlated electrons. After shortly summarising the existing theoretical results in this direction, I concentrate on the phenomena in doped manganites. I discuss general theoretical results on the phase separation at small doping and close to the doping x=0.5. The “global” phase diagram in this region is constructed. These general results are illustrated on the example of the particular system with rich and complicated properties — (LaPr)_1−xCa_xMnO₃, in which there exist a ferromagnetic metallic (FM) phase and a charge ordered (CO) insulating one. The experimental situation in this system is discussed and the interpretation is given in the framework of the model with competition of FM and CO, and the indications of phase separation and percolative nature of this system are given. The giant isotope effect observed in this situation is shortly discussed.     

Constraining the initial phase in water-fat separation

An algorithm is described for use in chemical shift-based water-fat separation to constrain the phase of both species to be equal at an echo time of zero. This constraint is physically reasonable since the initial phase should be a property of the excitation pulse and receiver coil only. The advantages of phase constrained water-fat separation, namely, improved noise performance and/or reduced data requirements (fewer echos), are demonstrated in simulations and experiments.     

Hydrophobic polymers modification of mesoporous silica with large pore size for drug release

Mesostructure cellular foam (MCF) materials were modified with hydrophobic polyisoprene (PI) through free radical polymerization in the pores network, and the resulting materials (MCF-PI) were investigated as matrices for drug storage. The successful synthesis of PI inside MCF was characterized by Fourier transform infrared (FT-IR), hydrogen nuclear magnetic resonance (¹H NMR), X-ray diffraction patterns (XRD) and nitrogen adsorption/desorption measurements. It was interesting to find the resultant system held a relatively large pore size (19.5 nm) and pore volume (1.02 cm³ g⁻¹), which would benefit for drug storage. Ibuprofen (IBU) and vancomycin were selected as model drugs and loaded onto unmodified MCF and modified MCF (MCF-PI). The adsorption capacities of these model drugs on MCF-PI were observed increase as compared to that of on pure MCF, due to the trap effects induced by polyisoprene chains inside the pores. The delivery system of MCF-PI was found to be more favorable for the adsorption of IBU (31 wt%, IBU/silica), possibly attributing to the hydrophobic interaction between IBU and PI formed on the internal surface of MCF matrix. The release of drug through the porous network was investigated by measuring uptake and release of IBU.     

Diffusion exchange NMR spectroscopy in inhomogeneous magnetic fields

Two-dimensional diffusion exchange experiments in the presence of a strong, static magnetic field gradient are presented. The experiments are performed in the stray field of a single sided NMR sensor with a proton Larmor frequency of 11.7 MHz. As a consequence of the strong and static magnetic field gradient the magnetization has contributions from different coherence pathways. In order to select the desired coherence pathways, a suitable phase cycling scheme is introduced. The pulse sequence is applied to study diffusion as well as the molecular exchange properties of organic solvents embedded in a mesoporous matrix consisting of a sieve of zeolites with a pore size of 0.8 nm and grain size of 2 μm. This pulse sequence extends the possibilities of the study of transport properties in porous media, with satisfying sensitivity in measurement times of a few hours, in a new generation of relatively inexpensive low-field NMR mobile devices.     

The role of etched silicon channels on the pore ordering of mesoporous silica: The importance of film thickness on providing highly orientated and defect-free thin films

If mesoporous thin films (MTFs) are to be utilised in device applications it is important that we produce films which not only possess a single pore direction across large substrate areas (in the range of microns) but are also relatively defect free. In this paper we report the use of confining architectures in the form of topographically patterned rectangular section channels etched into native silicon substrates to promote ordering of the mesopores. We discuss the effects of the channels on films with different thicknesses. The film thickness is shown to be a critical parameter in defining highly orientated and defect-free films and the data demonstrate that it is possible to achieve a single mesoporous silica domain across macroscopic dimensions with thin film thicknesses of approximately 200 nm but that critically pore order can be lost in ultra thin and thicker films produced by these methods.     

Topology and numerical simulation of phase separation in sodium silicate glasses

Liquid/liquid phase separation in glasses may lead to heterogeneities in the nanometer scale. The droplet phase can be nucleated from a homogeneous liquid. The chemical composition of the nanoscale phase separation changes with temperature in contrast to the nanocrystallization. The understanding of topological changes in the glass networks is of importance for the changes in viscosity and the microscopic changes in the growth rate during the course of the phase separation process. This work considers a glass system in which one of the separated phases is much more rigid than the other and the formed new phase possesses a lower viscosity in comparison to the matrix phase. The chemical composition of the matrix changes only in a thin layer around the growing droplets. A shell with increased rigidity is formed which decelerates the growth by encapsulation.     

Low-and high-dimension limits of a phase separation model

We study a simple zero-temperature model for phase separation of a binary alloy, in which nearest-neighbor interchange can occur if the fraction of AB pairs is not thereby increased. We present analytic results for the one-dimensional case and numerical results for the infinite dimensionality limit on a Cayley tree. In neither limit does the final fraction of AB pairs agree with the dimension-independent result found previously ind=3, 4, 5.     

On the local structure of the phase separation line in the two-dimensional Ising system

We investigate the structure of the phase separation line between the pure phases in the two-dimensional Ising model, the liquid and vapor phase in lattice gas language, at low temperatures. The fluctuations in the location of this line are known to diverge in the thermodynamic limit, something which is also believed to happen to the continuum liquid-vapor interface in three dimensions (in the absence of the gravitational field). We show that despite this global divergence it is possible to define precisely the local structure of the phase separation line. This has a finite, exponentially small, width at low temperatures which is related by a central limit theorem⁽¹⁾ to the width of the global fluctuations on the appropriate (divergent) length scale. The latter has been computed explicitly⁽²⁾ for all temperatures below the critical temperatureT _c, where it diverges as (T _c –T)^–1/2. We also prove a Gibbs formula for the surface tension at low temperature, which relates it to the local structure of the phase separation line.Supported in part by NSF grant No. M^rPHY 78-15920 and MCS78-01885.On leave from: Departement de Physique Théorique, Université de Louvain, Belgium.     

Assessment of pore structure parameters for polymer-templated mesoporous molecular sieves by means of nitrogen and argon adsorption

Pore size, wall thickness, and microporosity of polymer-templated mesoporous silica (PTMS) can be controlled by using different nonionic triblock copolymers as soft templates. The evolution of the pore structure of PTMS was studied by using nitrogen and argon adsorption at 77 K in addition to powder X-ray diffraction and transmission electron microscopy.     

Monte Carlo simulation of phase separation and clustering in the ABV model

As a model for a binary alloy undergoing an unmixing phase transition, we consider a square lattice where each site can be either taken by an A atom, a B atom, or a vacancy (V), and there exists a repulsive interaction between AB nearest neighbor pairs. Starting from a random initial configuration, unmixing proceeds via random jumps of A atoms or B atoms to nearest neighbor vacant sites. In the absence of any interaction, these jumps occur at jump rates _A and _B, respectively. For a small concentration of vacancies (c _v=0.04) the dynamics of the structure factorS(k,t) and its first two momentsk ₁(t),k ₂ ² (t) is studied during the early stages of phase separation, for several choices of concentrationc _B of B atoms. Forc _B=0.18 also the time evolution of the cluster size distribution is studied. Apart from very early times, the mean cluster sizel(t) as well as the moments of the structure function depend on timet and the ratio of the jump rates (= _B/ _A) only via a scaled timet/(). Qualitatively, the behavior is very similar to the direct exchange model containing no vacancies. Consequences for phase separation of real alloys are briefly discussed.     

The effect of silica nanoparticles on the pore structure of hydrating cement paste: a spatially resolved low-field NMR study

ABSTRACT

The hydration process of four different cement-based materials at different depths inside the sample was investigated using localised nuclear magnetic resonance relaxation measurements. All the samples are based on white Portland cement (CEM I 42.5 R), with a water-to-cement ratio of 0.5. One sample is a simple cement paste and the other three additionally contain 5% (by mass of cement) silica nanoparticles (50–200?nm size), silanised silica nanoparticles (with silane A 174) or silica fume (80% silica; 0.15?µm average size). The localised transverse relaxation measurements were performed using a single-sided NMR instrument. The relaxation rates were monitored for 48?h during the hydration process at different depths inside the sample. The results showed that the presence of nanoparticles influences not only the speed of hydration overall, but also the homogeneity of the materials.