De-mixing dynamics of a binary liquid system in a controlled-pore glass. A neutron spin-echo spectroscopy and small angle neutron scattering study

The temperature-induced microphase separation of the binary liquid system iso-butyric acid+heavy water (iBA + D(2)O) in a mesoporous silica glass (CPG-10-75) of nominal pore width 7.5 nm was investigated by neutron spin-echo spectroscopy (NSE) and neutron small-angle scattering (SANS). Two mixtures of different composition were studied at different scattering angles at temperatures above and below the bulk phase transition temperature. The phase separation in the pore space is found to occur at a lower temperature than the bulk transition and extends over a significant temperature range. The effective diffusion coefficient derived from NSE at low scattering angles is found to decrease by one order of magnitude from 70 degrees C to 20 degrees C. This observation is attributed to the growing size of concentration fluctuations having a cut-off at ca. 8 nm, which corresponds to the mean pore size. The dynamics of the concentration fluctuations appears to be strongly influenced by the confinement in the pores, as it differs strongly from the bulk behaviour. These results are consistent with the preliminary results of the SANS study.     

Self-diffusion in liquid lithium and lead from coherent quasi-elastic neutron scattering data

The temperature dependence of the self-diffusion coefficient of liquid lithium in the temperature range of 500–830 K has been investigated using coherent quasi-elastic neutron scattering. Good agreement with the results obtained from incoherent quasi-elastic neutron scattering experiments traditionally used for this purpose has been achieved, as well as with the corresponding literature data. In addition, one temperature point (623 K) has been obtained for the self-diffusion coefficient of liquid lead, which is a pure coherent scatterer.     

Detection of submicron-sized raft-like domains in membranes by small-angle neutron scattering

Using coarse grained models of heterogeneous vesicles we demonstrate the potential for small-angle neutron scattering (SANS) to detect and distinguish between two different categories of lateral segregation: 1) unilamellar vesicles (ULV) containing a single domain and 2) the formation of several small domains or “clusters” (~10 nm in radius) on a ULV. Exploiting the unique sensitivity of neutron scattering to differences between hydrogen and deuterium, we show that the liquid ordered (lo) DPPC-rich phase can be selectively labeled using chain deuterated dipalymitoyl phosphatidylcholine (dDPPC), which greatly facilitates the use of SANS to detect membrane domains. SANS experiments are then performed in order to detect and characterize, on nanometer length scales, lateral heterogeneities, or so-called “rafts”, in ~30 nm radius low polydispersity ULV made up of ternary mixtures of phospholipids and cholesterol. For 1:1:1 DOPC:DPPC:cholesterol (DDC) ULV we find evidence for the formation of lateral heterogeneities on cooling below 30 °C. These heterogeneities do not appear when DOPC is replaced by SOPC. Fits to the experimental data using coarse grained models show that, at room temperature, DDC ULV each exhibit approximately 30 domains with average radii of ~10 nm.     

Small-angle neutron and dynamic light scattering study of gelatin coacervates

The state of intermolecular aggregates and that of folded gelatin molecules could be characterized by dynamic laser light and small-angle neutron scattering experiments, which implied spontaneous segregation of particle sizes preceding coacervation, which is a liquid-liquid phase transition phenomenon. Dynamic light scattering (DLS) data analysis revealed two particle sizes until precipitation was reached. The smaller particles having a diameter of ～50 nm (stable nanoparticles prepared by coacervation method) were detected in the supernatant, whereas the inter-molecular aggregates having a diameter of ～400 nm gave rise to coacervation. Small-angle neutron scattering (SANS) experiments revealed that typical mesh size of the networks exist in polymer dense phase (coacervates) [1]. Analysis of the SANS structure factor showed the presence of two length scales associated with this system that were identified as the correlation length or mesh size, ξ = 10.6 Å of the network and the other is the size of inhomogeneities = 21.4 Å. Observations were discussed based on the results obtained from SANS experiments performed in 5% (w/v) gelatin solution at 60°C (ξ = 50 Å, ζ = 113 Å) and 5% (w/v) gel at 28°C (ξ = 47 Å, ζ = 115 Å) in aqueous phase [2] indicating smaller length scales in coacervate as compared to sol and gel.     

Collective dynamics and self-diffusion in a diblock copolymer melt in the body-centered cubic phase

The structure and dynamics of a strongly asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) (PEP-PDMS) diblock copolymer in the melt have been studied over a wide temperature range. Small-angle neutron scattering reveals that the sample exhibits two stable phases in this temperature range: Above the order-to-disorder transition temperature, it is disordered, whereas the domain structure is body-centered cubic (bcc) below, being stable down to the lowest temperatures measured. In the disordered state, dynamic light scattering (DLS) in the polarized geometry reveals the heterogeneity mode and the cluster mode. In the bcc phase, the PEP and the PDMS blocks form the micellar cores and the matrix, respectively. Here, two modes are observed in DLS, and the diffusion coefficients measured using pulsed field gradient (PFG) NMR are broadly distributed with the most probable diffusion coefficient coinciding with the slow DLS mode. We attribute the fast process in the bcc state to concentration fluctuations of the micellar cores (PEP), relaxing by mutual diffusion of the micelles with copolymers dissolved in the PDMS matrix. The slower process in the bcc state is ascribed to activated long-range self-diffusion of single copolymers from micelle to micelle through the PDMS matrix. This assignment is corroborated by the good coincidence of the reduced diffusivities with the ones from the literature. However, this mode may also be assigned to the rearrangement of entire micelles.This paper is dedicated to the memory of G. Fleischer     

Step-addition Method for Enhancing the Yield of Gold Nanoparticles in Block Copolymer Solution

Triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) has been used to synthesize gold nanoparticles from hydrogen tetrachloroaureate (III) hydrate (HAuCl₄·3H₂O) salt in aqueous solution at room temperature. Measurements were performed using the triblock copolymer Pluronic P85 (EO₂₆PO₃₉EO₂₆) at a fixed concentration (1 wt%) mixed with varying HAuCl₄·3H₂O concentration in the range of 0.001 to 0.1 wt%. The surface plasmon resonance (SPR) band in UV-visible absorption spectra confirmed the formation of the gold nanoparticles. The maximum yield of the nanoparticles was found at 0.005 wt% of the salt solution. Small-angle neutron scattering (SANS) does not show any significant change in the scattering profile in these suspensions of the nanoparticles. A similar behavior was also observed in dynamic light scattering (DLS) experiments where autocorrelation function was found to be independent of the salt concentration. This can be understood since a high-block copolymer-to-gold ion ratio (r ～ 22) is required in the reduction reaction to produce gold particles. As a result, a very small fraction of the block copolymers were associated with the gold nanoparticles, and hence lead to a very low yield. Both SANS and DLS basically see the micelles of most of these block copolymers, which are not associated with nanoparticles. Based on this explanation, a step-addition method was used to enhance the yield of gold nanoparticles by manifold, where the gold salt is added in small steps to maintain higher value of r (>22), and therefore continuous formation of nanoparticles.     

Investigation on pore structure and small-scale agglomeration behaviour in liquid phase sintered SiC using small angle neutron scattering

Mesoscopic density fluctuations in liquid phase sintered silicon carbide have been investigated using small angle neutron scattering (SANS). The increase in the additives results in the modification in the pore size distribution and to some extent the total porosity. SANS revealed a mass fractal nature of the agglomerated matrix microstructure. The fractal dimension of the matrix does not change appreciably with the additives although the upper cut-off value of the fractal decreases significantly with the increase in the additives. The liquid phase sintering due to the presence of additives helps to achieve higher level of densification. However, the agglomeration hinders achievement of the fully dense pellets.      

Critical anomaly and finite size scaling of the self-diffusion coefficient for Lennardben Jones fluids by non-equilibrium molecular dynamic simulation

We use non-equilibrium molecular dynamics simulations to calculate the self-diffusion coefficient, D, of a Lennard-Jones fluid over a wide density and temperature range. The change in self-diffusion coefficient with temperature decreases by increasing density. For density ρ^* = ρσ³ = 0.84 we observe a peak at the value of the self-diffusion coefficient and the critical temperature T^* = kT/ε = 1.25. The value of the self-diffusion coefficient strongly depends on system size. The data of the self-diffusion coefficient are fitted to a simple analytic relation based on hydrodynamic arguments. This correction scales as N^-α, where α is an adjustable parameter and N is the number of particles. It is observed that the values of α < 1 provide quite a good correction to the simulation data. The system size dependence is very strong for lower densities, but it is not as strong for higher densities. The self-diffusion coefficient calculated with non-equilibrium molecular dynamic simulations at different temperatures and densities is in good agreement with other calculations from the literature.     

Molecular dynamics study on water self-diffusion in aqueous mixtures of methanol,ethylene glycol and glycerol: investigations from the point of view of hydrogen bonding

Molecular dynamics simulations have been performed to investigate the aqueous binary mixtures of alcohols, including methanol, ethylene glycol (EG) and glycerol of molalities ranging from 1 to 5 m at the temperatures of 273, 288 and 298 K, respectively. The primary purpose of this paper is to investigate the mechanism of water self-diffusion in water-alcohol mixtures from the point of view of hydrogen bonding. The effects of temperature and concentration on water self-diffusion coefficient are evaluated quantitatively in this work. Temperature and concentration to some extent affect the hydrogen bonding statistics and dynamics of the binary mixtures. It is shown that the self-diffusion coefficient of water molecules decreases as the concentration increases or the temperature decreases. Moreover, calculations of mean square displacements of water molecules initially with different number n of H-bonds indicate that the water self-diffusion coefficient decreases as n increases. We also studied the aggregation of alcohol molecules by the hydrophobic alkyl groups. The largest cluster size of the alkyl groups clearly increases as the concentration increases, implying the emergence of a closely connected network of water and alcohols. The clusters of water and alcohol that interacted could block the movement of water molecules in binary mixtures. These findings provide insight into the mechanisms of water self-diffusion in aqueous binary mixtures of methanol, EG and glycerol.     

Theory of XMCD spectra at the L2,3 absorption edges of mixed valence Ce and Yb compounds in high magnetic fields

We examine the structure of aggregates formed due to DNA interaction with dipalmitoylphosphatidylcholine (DPPC) in presence of Ca²⁺ and Zn²⁺ using small-angle synchrotron X-ray diffraction (SAXD) and neutron scattering (SANS). SAXD shows structural heterogeneity as a function of the cation concentration and temperature: At low cation concentration (∼1 mM), aggregates show two DPPC phases, one with a lateral segregation of DNA and cation, while higher cation concentration improves the DNA packing and the condensed lamellar phase is observed in DNA+DPPC+20mMion²⁺ aggregates. The SANS detected the dissolution of the condensed lamellar phase into unilamellar DPPC+Zn²⁺ vesicles due to gel ↦ liquid-crystal phase transition in DNA+DPPC+20mM Zn²⁺ aggregates with the short fragmented salmon sperm DNA.     

Low-temperature interface between the gas and solid phases of hard spheres with a short-ranged attraction

At low temperature, spheres with a very short-ranged attraction exist as a near-close-packed solid coexisting with an almost infinitely dilute gas. We find that the ratio of the interfacial tension between these two phases to the thermal energy diverges as the range of the attraction tends to zero. The large tensions when the interparticle attractions are short ranged may be why globular proteins only crystallize over a narrow range of conditions.     

Dynamic crossover in hydration water of curing cement paste: the effect of superplasticizer

The influence of a new comb-shaped polycarboxylate-based superplasticizer (CSSP) on the hydration kinetics and transport properties of aged cement pastes has been investigated by high-resolution quasi-elastic neutron scattering (QENS) and low temperature differential scanning calorimetry (LT-DSC). A new method of analysis of QENS spectra is proposed. By applying the refined method we were able to access to four independent physical parameters including the self-diffusion coefficient of the hydration water confined in the cement paste. Mean squared displacement (MSD) of the hydrogen atom for mobile water molecules displays a dynamic crossover temperature in agreement with DSC data. The experimental results indicate that CSSP polymer added into cement paste moderates the hydration process and decreases the dynamic crossover temperature of the hydration water.     

Nano-meter-sized domain formation in lipid membranes observed by small angle neutron scattering

Using a contrast matching technique of small angle neutron scattering (SANS), we have investigated a phase separation to liquid-disordered and liquid-ordered phases on ternary small unilamellar vesicles (SUVs) composed of deuterated-saturated, hydrogenated-unsaturated phosphatidylcholine lipids and cholesterol, where the equilibrium size of these domains is constrained to less than 10nm by the system size. Below a miscibility temperature, we observed characteristic scattering profiles with a maximum, indicating the formation of nano-meter-sized domains on the SUVs. The observed profiles can be described by a multi-domain model rather than a mono-domain model. The nano-meter-sized domain is agitated by thermal fluctuations and eventually ruptured, which may result in the multi-domain state. The kinetically trapped nano-meter-sized domains grow to a mono-domain state by decreasing temperature. Furthermore, between the miscibility and disorder-order transition temperature of saturated lipid, the integrated SANS intensity increased slightly, indicating the formation of nano-meter-sized heterogeneity prior to the domain nucleation.     

SANS response of VVER440-type weld material after neutron irradiation,post-irradiation annealing and reirradiation

It is well accepted that the reirradiation behaviour of reactor pressure vessel (RPV) steel after annealing can be different from the original irradiation behaviour. We present the first small-angle neutron scattering (SANS) study of neutron irradiated, annealed and reirradiated VVER440-type RPV weld material. The SANS results are analyzed both in terms of the size distribution of irradiation-induced defect/solute atom clusters and in terms of the ratio of total and nuclear scattering intensity in a saturation magnetic field (A ratio). The measured A ratio is compared with calculations performed on the basis of the cluster composition reported for a similar weld material investigated by means of three-dimensional atom probe field ion microscopy. The observed deviation between both estimates and possible reasons for the discrepancy are discussed. Special emphasis is placed on the differences between the materials response to the original irradiation and to reirradiation after annealing. The results indicate that reirradiation-induced clusters are slightly different in their average composition and their formation saturates at a lower volume fraction than in the case of the original irradiation.     

The curvature of the self-diffusion Arrhenius plot through the mono-vacancy mechanism

We present a new formalism for the explanation of the curvature of the Arrhenius self-diffusion plots on the basis of mono-vacancy diffusion mechanism. The temperature dependence of the diffusion coefficient appears from the concentration dependence of the vacancy formation energy and without any additional assumption about a particular diffusion mechanism. This method gives a possibility to estimate different parameters of the self-diffusion process from first principles in an assumption that vacancies form a random solid solution of holes in the bulk of the crystal. We apply this formalism to the analysis of the curvature of the Arrhenius plot as well as to the estimation of other parameters of self-diffusion inbcc Cs. The numerical evaluations are based on the Full Potential Linearized Muffin-Tin Orbitals method of the calculation of total energies.     

氯化钠水溶液结构的研究

利用上海光源(SSRF)的第三代同步辐射光源测定室温下摩尔浓度分别为0.172 mol/L、0.343 mol/L、0.699 mol/L、1.064 mol/L、2.832 mol/L、3.910 mol/L、5.289 mol/L的NaCl水溶液的X射线散射数据。由X射线散射数据可知,随着NaCl水溶液浓度的增大,X射线散射曲线的特征峰由12.6°到13.4°发生偏移。运用Pair Distribution Function(PDF)理论对X射线散射数据进行处理,得到了不同浓度NaCl水溶液及纯水的差值对分布函数,其中的O-O峰随着浓度的增大逐渐分裂为两峰,O-O峰位在0.282 nm处。利用分子动力学模拟研究不同浓度的NaCl水溶液,表明Na+、Cl-的引入对水分子的氢键结构有一定的破坏,当浓度大于15%时,这种效果尤其明显。Na+、Cl-均存在两层水化层,各离子间配位数随浓度的增大而减少。H2O分子的自扩散系数远大于Na+和Cl-的自扩散系数,后两者的值随浓度的增大逐渐减少,Na+和Cl-的水化半径均随浓度增大而降低。     

Equilibrium cluster phases and low-density arrested disordered states: the role of short-range attraction and long-range repulsion

We study a model in which particles interact with short-ranged attractive and long-ranged repulsive interactions, in an attempt to model the equilibrium cluster phase recently discovered in sterically stabilized colloidal systems in the presence of depletion interactions. At low packing fractions, particles form stable equilibrium clusters which act as building blocks of a cluster fluid. We study the possibility that cluster fluids generate a low-density disordered arrested phase, a gel, via a glass transition driven by the repulsive interaction. In this model the gel formation is formally described with the same physics of the glass formation.     

Self-diffusion in liquid lithium from coherent quasielastic neutron scattering

Using the method of quasielastic coherent neutron scattering by liquid lithium, the temperature dependence of self-diffusion coefficient is investigated and compared with analogous data extracted by the incoherent scattering method.     

Self-diffusion of multiarm star polymers in solution far from and near the ordering transition

The self-diffusion of three 128-arm polybutadiene star solutions in toluene was investigated over a broad concentration range from dilute to the ordering region with pulsed field gradient NMR (PFG-NMR). The strong concentration dependence of the self-diffusion coefficient in the fluid state is distinguished clearly from that of linear chains and can be described by a non-Arrhenius VFT-like equation with the concentration playing the role of inverse temperature. In the concentrated regime, the observation of two dynamic phases reflects the coexistence of crystalline and liquid phases over a limited concentration region. The concentration dependences of both the ordinary (fluid-like) diffusion and the completely restricted in-cage motion of these hyper stars are in agreement with the behavior of concentrated colloidal suspensions.     

Composition of cementite in the dependence on the temperature. In situ neutron diffraction study and Ab initio calculations

The structure state of carbon eutectoid steel has been studied by the in situ neutron diffraction method in the temperature range from room temperature to 800°C. It has been shown that an increase in the temperature is accompanied by a decrease in the concentration of carbon in cementite, whereas its weight fraction and the parameters of the orthorhombic lattice change slightly. The ab initio calculations of the nonstoichiometric carbides Fe₃C _x (0 < x < 1) indicate that the structure of cementite remains stable upon the appearance of vacancies in the carbon sublattice with a relatively low formation energy. Thus, cementite should be considered as an interstitial phase Fe₃C _x with a wide homogeneity range.