Hydrodynamic-flow-driven phase evolution in a polymer blend film modified by diblock copolymers

We have studied surface-directed phase separation in thin films of deuterated polystyrene and poly(bromostyrene) (with 22.7% of monomers brominated) using ³He nuclear reaction analysis, dynamic secondary ion mass spectroscopy and atomic force microscopy combined with preferential dissolution. The crossover from competing to neutral surfaces of the critical blend film (cast onto Au) was commenced: polyisoprene-polystyrene diblock copolymers were added and segregated to both surfaces reducing in a tuneable manner the effective interactions. Two main stages of phase evolution are characterised by i) the growth of two surface layers and by ii) the transition from the four-layer to the final bilayer morphology. For increasing copolymer content the kinetics of the first stage is hardly affected but the amplitude of composition oscillations is reduced indicating more fragmented inner layers. As a result, a faster mass flow to the surfaces and an earlier completion of the second stage were observed. The hydrodynamic flow mechanism, driving both stages, is evidenced by nearly linear growth of the surface layer and by mass flow channels extending from the surface layer into the bulk. The final bilayer structure, formed even for the surfaces covered by strongly overlapped copolymers, is indicative of long-range (antisymmetric) surface forces. Received 15 March 2000 and Received in final form 9 February 2001     

Molecular simulation studies of self-assembled monolayers of alkanethiols on Au(111)

A review is presented of this group's recent molecular simulation studies of self-assembled monolayers (SAMs) of alkanethiols on Au(111) surfaces. SAMs are very useful for the systematic alteration of the chemical and structural properties of a surface by varying chain length, tail group and composition. The scientific and technological importance of SAMs cannot be overestimated. The present work has been centred on studies of atomic scale surface properties of SAMs. First, configurational-bias Monte Carlo simulations were performed in both semigrand canonical and canonical ensembles to investigate the preferential adsorption and phase behaviour of mixed SAMs on Au(111) surfaces. Second, a novel hybrid molecular simulation technique was developed to simulate atomic force microscopy (AFM) over experimental timescales. The method combines a dynamic element model for the tip-cantilever system in AFM and a molecular dynamics relaxation approach for the sample. The hybrid simulation technique was applied to investigate atomic scale friction and adhesion properties of SAMs as a function of chain length. Third, dual-control-volume grand canonical molecular dynamics (DCV-GCMD) simulations were performed of transport diffusion of liquid water and methanol through a slit pore with both inner walls consisting of Au(111) surfaces covered by SAMs under a chemical potential gradient. Surface hydrophobicity was adjusted by varying the terminal group of CH₃ (hydrophobic) or OH (hydrophilic) of the SAMs. Finally, ab initio quantum chemical calculations were performed on both clusters and periodic systems of methylthiols on Au(111) surfaces. Based on the ab initio results, an accurate force field capable of predicting c(4×2) superlattice structures over a wide range of temepratures for alkanethiols on Au(111) was developed. The extension of current work is discussed briefly.     

硫醇自组装分子膜末端基团对其电荷输运特性的影响

在金(111)表面组装了具有不同末端基团的硫醇单层分子膜，并利用导电原子力显微镜研究了分子膜的电输运性质，发现不同末端基团的分子自组装膜的导电能力有明显差别.结合X射线光电子能谱，研究了末端基团中碳原子的结合能与相应硫醇分子电导的关系.结果表明不同末端基团分子膜导电能力的差别可归结为末端基团碳原子电子结合能的差异.结合能越高，末端基团电子的局域化程度越强，导致电子有效注入分子主链的势垒越高，从而减弱了分子膜对电子的输运能力.此外，实验还发现不同末端基团的硫醇单层分子膜有不同的表面电势，导致分子膜电流电压特性曲线的零点产生偏离. 关键词： 分子自组装膜 输运特性 末端基团 导电原子力显微镜     

Measuring the implantation depth of silver clusters in graphite

Scanning tunnelling microscopy (STM) and molecular dynamics (MD) simulations have been used to investigate the implantation of Ag₇ ^- clusters into the graphite surface. An experimental measure of the implantation depth of individual clusters is gained via thermal oxidation of the bombarded graphite surfaces. This process results in etching of the cluster-induced defects to form etch pits which grow laterally whilst retaining the depth of the implanted cluster. STM imaging of the etch pits reveals the distribution of implantation depths for deposition energies of 2 keV and 5 keV. Molecular dynamics simulations for clusters of 5 keV energy show that the implantation depth for Ag₇ ^- is largely independent of the impact site on the graphite surface and the cluster orientation. The implantation depth found by MD lies at the upper edge of the experimental depth distribution. Received 30 November 2000     

Branched crystal morphology of linear polyethylene crystallized in a two-dimensional diffusion-controlled growth field

The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d _f = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5^° around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200) regions are quite different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot. Received 15 March 2002 and Received in final form 29 April 2002     

Shear-induced ordering of lamellar and gyroid structures observed in a nonionic surfactant/water system

The shear-induced ordering of lamellar and gyroid structures of a nonionic surfactant C₁₆E₇/D₂O system in a Couette shear cell ( 0.001 < < 10 s^-1, : shear rate) has been investigated by using a small angle neutron scattering technique. In the lamellar phase, the steady shear flow having > 0.01 s^-1 suppresses undulation fluctuations of lamellae (Maxwell effect). This suppression of fluctuations brings two effects; 1) shear-induced lamellae ordering toward a parallel orientation and 2) obstruction of a lamellar↦gyroid transition. It is quite interesting to note that there is a characteristic shear rate range ( 0.01 < < 0.3 s^-1), where both effects take place. We have also investigated the shear effects on the gyroid phase. Below the characteristic shear rate range, the gyroid structure keeps three-dimensional network lattice, while above the characteristic shear rate range, the gyroid structure transforms to the parallel orientation lamellae (shear-induced gyroid-lamellar transition). Thus the shear flow having the characteristic shear rate plays very important roles in shear ordering phenomena. Received 26 June 2000 and Received in final form 12 January 2001     

Magnetic reconstructions at the surface of the B2 FeV alloy

We present an ab initio study of the magnetic surface reconstructions of the B2 FeV alloy using a self-consistent tight-binding linearized muffin tin orbital method developed in the atomic spheres approximation. For (001) and (111), the surface reconstruction stabilizes configurations unstable in the bulk alloy. When Fe is at the (001) surface, a c(2×2) in-plane antiferromagnetic order is found to be the ground state with magnetic moments of -2.32 and 2.27. A p(1×1) ↓ ferromagnetic order is displayed in case of V toplayer with a magnetic moment of -1.83. At the (111) surface, we obtain for Fe toplayer two solutions p(1×1)↑ and p(2×1). The configuration p(1×1)↑ is found to be the ground state with a magnetic moment per atom of 2.34. For V toplayer, only the p(1×1) ↓ solution is obtained with a moment of -0.84. In all cases, the Fe-V coupling is always antiparallel like in the bulk. Our results are discussed and compared to experiments. Received 11 August 2000 and Received in final form 8 June 2001     

Debye-Hückel theory for slab geometries

The electrostatic interaction of charged particles through or at a low-dielectric slab, such as a lipid bilayer immersed in water or a self-assembled monolayer (SAM) on a metal substrate, is considered theoretically in the presence of salt within the Gaussian approximation using a generalized Green's formalism. A number of separate situations are discussed: i) The presence of a low-dielectric slab leads to pronounced interactions of a single charge with the slab via the formation of polarization surface charges. For SAMs on metal substrates, there is an intricate crossover from image-charge attraction to the metal substrate (for large distances) to image-charge repulsion from the SAM (for small distances) with a stable minimum at a distance of roughly 20 times the thickness of the hydrophobic film. For bilayers in water, the interaction of a single charge is always repulsive. ii) The surface potential of a SAM is calculated for the case when the hydrophobic layer contains dipole moments, which might explain the recently observed long-ranged repulsion of hydrophobic scanning tips from PEG-terminated SAMs on gold. iii) The interaction between charged particles through the bilayer is weakened. Oppositely charged particles still attract each other through the membrane. The free-energy minimum occurs as a result of the competition between self-repulsion from the slab and interparticle attraction and is located at a separation from the membrane surface which equals 15 times the membrane thickness. iv) Surface charges on the two surfaces of a bilayer attract each other through the bilayer unless the surface charge densities are the same, even if the signs are the same. v) All these effects are strongly influenced by the presence of salt. Received 25 January 2000     

Determination of molecular orientation in ultrathin liquid crystal. films on solid substrates using X-ray absorption spectroscopy

42 H₆₀O₆, HBT) deposited on a (111)-oriented Au single crystal and a polycrystalline indium tin oxide (ITO) substrate has been carried out using X-ray absorption spectroscopy. Films of thicknesses between 2 nm and 15 nm were prepared in UHV by evaporation of HBT [which exhibits a discotic liquid crystalline (LC) bulk phase] from a Knudsen cell. Thickness and composition of the HBT films were determined using X-ray photoelectron spectroscopy (XPS). For the thinnest films with thicknesses in the monolayer regime, the orientational analysis reveals a pronounced orientation of the disc-shaped HBT molecules parallel to the Au surface. For thicker films, a significantly reduced anisotropy is observed with the molecular plane oriented more normal to the Au surface. In the case of the ITO-substrates, no significant differences were observed between different thickn esses and the average orientation of the molecular planes was predominantly normal to the surfaces, as for the thicker films on the Au substrate. Received: 1 March 1997/Accepted: 24 April 1997     

A molecular theory of smectic C liquid crystals made of rod-like molecules

Organic compounds exhibiting the smectic C phase are made of rod-like molecules that have dipolar groups with lateral components. We argue that the off-axis character of the lateral dipolar groups can account for tilt in layered smectics (SmC, SmC*, SmI etc.). We develop a mean-field theory of the smectic C phase based on a single-particle potential of the form U _C ∝ sin(2θ)cosφ, consistent with the biaxial nature of the phase, where θ and φ are the polar and azimuthal angles, respectively. The hard-rod interactions that favour the smectic A phase with zero tilt angle are also included. The theoretical phase diagrams compare favourably with experimental trends. Our theory also leads to the following results: i) a first-order smectic C to smectic A transition above some value of the McMillan parameter α, leading to a tricritical point on the smectic C to smectic A transition line and ii) a first-order smectic C to smectic C transition over a very small range of values of the model parameters. We have also extended the theory to include the next higher-order term in the tilting potential and to include the effect of different tilt angles for the molecular core and the chain in the SmC phase. Received 3 August 2002 RID="a" ID="a"Present address: Department of Physics, Vijaya College, R. V. Road, Bangalore - 560 004, India. RID="b" ID="b"e-mail: nvmadhu@rri.res.in     

Ab initio calculation of Electron Energy Loss spectra of clean and 1ML Fe-covered Ni(111)

The dielectric and the loss functions of Ni(111) are calculated by the Full Potential Linear Muffin Tin Orbitals (FPLMTO) ab initio method whithin the three-layers model (vacuum/surface/bulk). Particular attention is devoted to determine surface and bulk state contributions to the spectra. Good agreement is found with recent experimental EELS data on the Fe-covered Ni(111) surface. Received 10 July 2002 Published online 19 November 2002     

The timescale of spinodal dewetting at a polymer/polymer interface

We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate) (PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface. Received 25 June 2001 and Received in final form 5 December 2001     

Grain growth and phason-strain field in quasicrystalline Al-Li-Cu

We report on grain growth and related structure change in single phased Al-Li-Cu quasicrystals. The icosahedral phase grains have been investigated using scanning ion microscopy and transmission electron microscopy. Regular boundaries between large grains have been observed both before and after high temperature annealing. The electron diffraction study shows that the grain growth is accompanied by a reduction of the phason-strains. The orientation relation between grains sets the 2-fold icosahedral axes parallel, and the coincidence of the planes depends on the phason strain-field. The effect of phason-strain field on these boundaries is discussed. It is proposed that the phason strain elimination can play a role in the grain growth. Received 1 February 1999 and Received in final form 12 May 1999     

Steps and facets at the surface of soft crystals

We consider the shape of crystals which are soft in the sense that their elastic modulus μ is small compared to their surface tension γ, more precisely μa < γ where a is the lattice spacing. We show that their surface steps penetrate inside the crystal as edge dislocations. As a consequence, these steps are broad with a small energy which we calculate. We also calculate the elastic interaction between steps a distance d apart, which is a 1/d ² repulsion. We finally calculate the roughening temperatures of successive facets in order to compare with the remarkable shapes of lyotropic crystals recently observed by Pieranski et al. [#!Pieranski!#,#!EPJ!#]. Good agreement is found. Received 25 June 2001     

Effect of interfacial alloying on the surface plasmon resonance of nanocrystalline Au-Ag multilayer thin films

Nanocrystalline Au and Ag in multilayer thin film form with Au/Ag/Au structure were prepared by high pressure (∼40 Pa) d.c. sputtering techniques. The Ag concentrations in Ag_xAu_1-x films were changed from x = 0 to 1. These multilayer films with varying Ag concentration showed significant changes in microstructures obtained from TEM and XRD analyses. The optical absorption spectra of these multilayer films showed a single plasmon band confirming the formation of Au-Ag alloy. We ascribe this alloying to the interfacial reactions in nanophase limited at the Au-Ag interface. The red-shift and broadening of the plasmon bands with the increase in silver concentration could be associated to the increase in size of the nanoparticles and its distribution. The observed red shift in the plasmon band may be associated with the change in electronic structure at the Au-Ag interface due to configuration mixing of the atomic energy levels of Au and Ag. Received 17 October 2002 / Received in final form 26 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: msakp@mahendra.iacs.res.in     

Molecular dynamics of contact behavior of self-assembled monolayers on gold using nanoindentation

Molecular dynamics simulation is used to study nanoindentation of the self-assembled monolayers (SAMs) on an Au surface. The interaction of SAM atoms is described by a general universal force field (UFF), the tight-binding second-moment approximation (TB-SMA) is used for Au substrate, and the Lennard-Jones potential function is employed to describe interaction among the indenter, the SAMs, and the Au substrate atoms. The model consists of a planar Au substrate with n-hexadecanethiol SAM chemisorbed to the substrate. The simulation results show that the contact pressure increases as the SAMs temperature increases. In addition, the contact pressure also increases as the depth and velocity of indentation increase.     

Correlation between the viscoelastic properties of a soft crystal and its microstructure

We investigate the rheological properties of a cubic fcc phase of micelles obtained by aggregation of a triblock copolymer (PEO)₁₂₇(PPO)₄₈(PEO)₁₂₇ in water as selective solvent. The resulting soft solid is submitted to a range of stresses varying from 20 to 800Pa in Couette geometry. Creep and flow behaviour can be distinguished and interpreted in terms of structural changes previously observed by SAXS under flow. Contrasting with other systems, no discontinuity in the flow behaviour is associated with the structural changes. The strong shear thinning is interpreted from the scattering data, as resulting from the nucleation of a new structure of hexagonal compact planes parallel to the Couette walls. This creates a lubricating domain in the gap, whose size grows with the applied shear rate. We argue moreover that the very existence of flow (as a steady state opposed to creep) is associated with this so-called layer-sliding structure in a fraction, however small, of the sample. Received on 4 June 1999 and Received in final form 6 September 1999     

Confinement of columnar diblock copolymers: Simulations, theory and applications

The inherent nanoscale morphologies of self-organizing diblock copolymer melts are now being investigated for a variety of technological applications. To obtain global, well-oriented, regular patterns requires suitably confining and aligning the melt between two flat plates. Here we consider such confinement for an asymmetrical diblock melt, which forms columns of the minority phase in a matrix of the majority phase. We investigate this system with a combination of numerical simulations and strong segregation theory and make suggestions as to when perpendicular orientation should prevail over parallel orientation of the columns. Received 22 May 2001 and Received in final form 14 February 2002     

Growth velocity and the topography of Ni-Zn binary alloy electrodeposits

We show that the electrodeposition of Ni-Zn alloys at the lowest growth velocities, v < 0.5μm/s, exclusively proceeds from an abnormal co-deposition phenomenon. The growth process in this v region greatly depends on the initial [Co²⁺] concentration of the film deposition bath. A theoretical approach of this process including the role of the saturation surface roughness of the alloy, , leads to an estimation of the transport properties of the ad-atoms involved during the deposit formation. Their surface diffusion coefficient varying between 1.76×10^-10 and 2.40×10^-8 cm^-2/s exhibits a minimal value, D _s = 2.10×10^-10 cm^-2/s located between v = 0.17 and 0.35μm/s. The spatial scaling analysis of the local roughness, σ, examined according to the power-law σ≈L ^α reveals that the resulting roughness exponents concurs with the Kardar-Parisi-Zhang dynamics including the restricted surface diffusion. Two main v regions leads to different fractal textural features of the alloy film surface. Below 0.10 μm/s, the roughness exponent obtained is α≈ 0.6, depicting a limited ad-atom mobility. Over v = 0.30μm/s, this exponent stabilises at α≈ 0.82, indicating an increase of the surface diffusion. Received 16 August 2000 and Received in final form 20 June 2001     

Mobility in thin polymer films ranging from local segmental motion, Rouse modes to whole chain motion: A coupling model consideration

Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( ≈ 1.5 nm) films obtained by intercalating a polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of the local segmental relaxation time found experimentally. Received 1 August 2001 and Received in final form 1 December 2001