The polymer mat: Arrested rebound of a compressed polymer layer

The European Physical Journal E - Compression of an adsorbed polymer layer distorts its relaxed structure. Surface force measurements from different laboratories show that the return to this...     

Computer simulation of nanoindentation into polymer films

We present computer simulations of nanoindentation into amorphous polymer films. The bulk polymer is treated through a united atom model in connection with molecular dynamics methods. The dynamics of the indenter is modeled as overdamped, such that the indentation velocity is proportional to the difference between the external force acting onto the tool and the resistance force built up in the polymer film. We concentrate on the initial, kinetic stage of the indentation process and give results for the motion of the indenter, the deformation field of the polymer film, the stress field, and the field of total monomer energy. We propose an effective coefficient as a new measure for the resistivity of a surface against indentation. Its value can be determined in an experiment with constant indentation velocity. In addition, we investigate the free drift behavior when the external driving force has been set to zero and the tool is expelled from the polymer film. For different polymer chain lengths, the tool’s motion is exponential in time and we determine the relaxation scale.     

Probing chromosome structure with dynamic force relaxation

We report measurements of the dynamics of force relaxation in single mitotic chromosomes, following step strains applied with micropipettes of force constant approximately 1 nN/microm. The force relaxes exponentially after an elongation (l/l(0)) to less than 3x native length, with a relaxation time approximately 2 sec. This relaxation time corresponds to an effective viscosity approximately 10(5) times that of water. We experimentally rule out solvent flow into the chromosome as the mechanism for the relaxation time. Instead, the relaxation can be explained in terms of the disentanglement dynamics of approximately 80 kb chromatin loop domains.     

The Influence of Hydrogen Adsorption on Magnetic Properties of Ni/Cu(001) Surface

Ni/Cu(001) is known as a unique system showing the spin-reorientation transition from an in-plane to out-of-plane magnetization direction when the Ni-overlayer thickness is increased. We investigate different relaxed multilayer structures with a hydrogen adlayer using the full-potential linearized augmented plane-wave method. The relaxed geometries, determined by total energy and atomic force calculations, show that H-monolayer strongly influences the interlayer distance between the Ni-surface and sub-surface layers yielding the outward relaxation of Ni-layer at H/Ni interface. Furthermore, large decrease of local magnetic moments at the top surface area is found for the surface covered by H. The magneto-crystalline anisotropy energies are calculated for fully relaxed H/Ni-films. The spin-reorientation transition critical thickness of 4 ML is found in good quantitative agreement with the experiment.     

Thermal annealing effects on a compositionally graded SiGe layer fabricated by oxidizing a strained SiGe layer

Thermal annealing effects on a thin compositionally graded SiGe buffer layer on silicon substrate fabricated by oxidizing a strained SiGe layer are investigated with X-ray diffraction, ultraviolet Raman spectra and atomic force microscopy. Interestingly, we found that the surface roughness and the threading dislocation densities are kept low during the whole annealing processes, while the Ge concentration at the oxidizing interface decreases exponentially with annealing time and the strain in the layer is only relaxed about 66% even at 1000 °C for 180 min. We realized that the strain relaxation of such a compositionally graded SiGe buffer layer is dominated by Si-Ge intermixing, rather than generation and propagation of misfit dislocations or surface undulation.     

Dewetting as an investigative tool for studying properties of thin polymer films

Employing mass conservation, time-resolved dewetting experiments of thin polymer films allow to determine in real time the dynamic contact angle and the slippage length. Moreover, based on a systematic variation of interfacial properties of a polymer brush, dewetting makes it possible to calculate the force it needs to extract a single polymer chain from its own melt. In the visco-elastic regime close to the glass transition, the temperature and molecular weight dependence of the relaxation time of residual stresses resulting from film preparation by spin-coating can be obtained from the evolution of the shape of the dewetting rim. The presented examples demonstrate that dewetting represents a powerful approach for a sensitive characterization of rheological, frictional and interfacial properties of thin polymer films.     

Growth of Si whiskers by MBE: Mechanism and peculiarities

We analyzed the stress-driven mechanism of MBE Si whisker growth. It is shown that the driving force for MBE whisker growth is determined by the relaxation of elastic energy stored in the overgrown layer L_s due to gold intrusion. In this case the supersaturation is determined by the interplay between elastic stresses and surface energy. The latter is considerably decreased due to decoration of the Si surface by gold resulting in formation of thin liquid Si/Au eutectic layer. This suggests that in our case the Si supersaturation is not an independent growth parameter as it is in the chemical vapor deposition growth method. Instead it is determined by stress in the overgrown Si layer. This approach allows us to explain quite well the growth kinetic and the relationship between the radius and the length of the whiskers. The whisker growth in our case can be considered as a stress relaxation mechanism, where the stress relaxation occurs due to transition from the two-dimensional system to the three-dimensional one.     

PbTe(001)表面原子几何结构和电子结构的第一性原理计算

用第一性原理的密度泛函理论计算了PbTe（001）表面的几何结构和电子结构.计算结果表明：PbTe（001）表面不发生重构，但表面几层原子表现出明显的振荡弛豫现象，其中第一、第二层间距减小4.5%，第二、第三层间距增加2.0%，并且表面层原子出现褶皱.表面带隙在X 点，带隙变宽，在基本带隙中不引入新的表面态，而导带底和价带顶附近等多处出现新的表 面共振态；弛豫后费米面处态密度很低，所以表面结构很稳定. 关键词： 密度泛函理论 表面几何结构 表面电子结构 PbTe     

Real-time determination of the slippage length in autophobic polymer dewetting

We investigated the kinetics of autophobic dewetting, caused by differences in entropy, of a polymer melt slipping on a monolayer of end-grafted identical molecules (polymer brush). From simultaneous measures of the dewetted distance and the width of the resulting rim, we obtained in real time and quantitatively the slippage length and the contact angle, a measure of the "incompatibility" between identical molecules. Furthermore, we could directly relate a decrease in the slippage length in the course of the experiments at elevated temperatures to temporal or permanent attachment of polymers from the melt to the brush.     

Ion-beam crystallography of clean and sulfur covered Ni(110)

Medium energy ion scattering has been used to determine the atomic structure of a Ni(110) surface covered with 0.5 monolayer of sulfur. After having confirmed that the sulfur atom resides in a fourfold-coordinated hollow site, it was found that its distance above the plane of the first Ni layer is 0.87 ± 0.03 Å. We measured a 6 ± 3% outward relaxation effect for the sulfur covered Ni(110) surface layer and an inward relaxation of 4 ± 1% when this surface is clean.     

Deviations from liquidlike behavior in molten polymer films at interfaces

We have performed x-ray specular and diffuse scattering on liquid polymer films and analyzed the spectra as a function of film thickness and molecular weight. The results show that films whose molecular weight is close to the entanglement length behave as simple liquids except that the shortest wavelength is determined by the radius of gyration (R(g)) rather than the monomer-monomer distance. When the molecular weight is higher than the entanglement length, the strong deviations from liquidlike behavior are observed. We find that the long wavelength cutoff vector, q(l,c), scales with film thickness, d as d(-1.1+/-0.1) rather than the usual d(-2) expected for simple liquids. If we assume that these deviations are due to surface pinning of the polymer chains, then our results are consistent with the formalism developed by Fredrickson et al. to explain the capillary wave spectrum that can propagate in a polymer brush.     

Strain relaxation and surface morphology of high indium content InAlAs metamorphic buffers with reverse step

Low-temperature step-graded high indium content InAlAs (In% = 0.75) metamorphic buffer layers with reverse step layer grown on GaAs substrate by molecular beam epitaxy are investigated in this paper. The composition and the strain relaxation of the top InAlAs layer are determined by high-resolution triple-axis X-ray diffraction measurements, which show that the top InAlAs layer is nearly fully relaxed and the growth parameters for these samples have little influence on the strain relaxation ratio. Surface morphology is observed by reflection high-energy electron diffraction pattern and atomic force microscopy. The surface morphology is found to depend strongly on both the growth temperature and the As flux. Compared with other samples, the sample growth under the optimized conditions has the smallest value of root mean square surface roughness. Furthermore, the ω − 2θ and ω scans of the triple-axis X-ray diffraction and transmission electron microscopy result also show the sample grown under the optimized conditions has good crystalline quality.     

Collapse of spherical polyelectrolyte brushes in the presence of multivalent counterions

We consider the interaction of multivalent counterions with spherical polyelectrolyte brushes (SPB). The SPB result if linear polyelectrolyte (PE) chains (contour length: 60 nm) are densely grafted to colloidal spheres of 116 nm in diameter. Dispersed in water, the surface layer consisting of chains of the strong PE poly(styrene sulfonic acid) (PSS) will swell. We demonstrate that successive addition of trivalent ions (La3+) leads to a collapse in which the surface layer is shrinking drastically. All findings are discussed on the base of a theoretical mean-field approach using the Donnan equilibrium. The ion exchange and a strong binding of trivalent ions by PE chains is followed up by a drop in the osmotic pressure inside the brush. This reduction is the driving force for the collapse. The strong ion-chain correlation is discussed with results obtained from molecular dynamics simulations.     

熵驱动下柱状高分子刷螺旋结构的研究

自然界中广泛存在螺旋结构,在特定情形下熵能驱动高分子链形成螺旋结构.本文采用分子动力学方法研究柱状高分子刷吸附在无限长圆柱表面时的构象行为.发现其构象与嫁接支链条数、柱状高分子刷与圆柱表面之间的吸附能密切相关.在较弱的吸附能下,具有较多支链条数的柱状高分子刷能形成完整的螺旋结构,其本质就是熵驱动下形成的螺旋结构.该研究有助于加深对生物大分子螺旋结构的理解.     

Multiple time scales in diffraction measurements of diffusive surface relaxation

We grew SrTiO3 on SrTiO3(001) by pulsed laser deposition, using x-ray scattering to monitor the growth in real time. The time-resolved small-angle scattering exhibits a well-defined length scale associated with the spacing between unit-cell high surface features. This length scale imposes a discrete spectrum of Fourier components and rate constants upon the diffusion equation solution, evident in multiple exponential relaxation of the "anti-Bragg" diffracted intensity. An Arrhenius analysis of measured rate constants confirms that they originate from a single activation energy.     

Dynamical process of complex systems and fractional differential equations

Behavior of dynamical process of complex systems is investigated. Specifically we analyse two types of ideal complex systems. For analysing the ideal complex systems, we define the response functions describing the internal states to an external force. The internal states are obtained as a relaxation process showing a “power law” distribution, such as scale free behaviors observed in actual measurements. By introducing a hybrid system, the logarithmic time, and double logarithmic time, we show how the “slow relaxation” (SR) process and “super slow relaxation” (SSR) process occur. Regarding the irregular variations of the internal states as an activation process, we calculate the response function to the external force. The behaviors are classified into “power”, “exponential”, and “stretched exponential” type. Finally we construct a fractional differential equation (FDE) describing the time evolution of these complex systems. In our theory, the exponent of the FDE or that of the power law distribution is expressed in terms of the parameters characterizing the structure of the system.     

Probing slow dynamics in supported thin polymer films

We have used variable cooling rate ellipsometric measurements to probe the slow dynamics in thin supported polystyrene films. For the slowest cooling rates (approximately 1 K/min) the measured Tg values are reduced below the bulk value with the measured Tg of 341 K for a 6 nm film. As the cooling rate is increased the Tg reductions become smaller until at cooling rates >90 K/min there is only slight evidence for a film-thickness-dependent Tg value. By relating the cooling rate to a relaxation time, we show that the relaxation dynamics of the thin films appears to become Arrhenius with an activation energy that decreases with decreasing film thickness. We discuss this in terms of a possible connection to a length scale for cooperative motion. Finally, the results can be used to resolve a number of outstanding contradictory reports in the literature.     

Structural relaxation of Zr_(41)Ti_(14)Cu_(12.5)Ni_(10)Be_(22.5) bulk metallic glass under high pressure

Zr41Ti14Cu12.5Ni10Be22.5bulk metallic glass (BMG) is annealed at 573 K under 3 GPaand its structural relaxation is investigated by X-ray diffraction, ultrasonic study, compression as well as sliding wear measurements. It is found that after the ZrTiCuNiBe BMG sample was annealed under high pressure, the mechanical properties were improved. Moreover, the BMG with relaxed structure exhibits markedly different acoustic properties. These results are attributed to the fact that relaxation under high-pressure results in a microstructural transformation in the BMG.     

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     

Low-frequency proton NMR relaxometry of a polymer dispersed liquid crystal above TNI

Using proton NMR relaxometry in the kilohertz frequency range, we study dynamics of 5CB liquid crystal molecules dispersed in the form of spherical microdroplets in a PDLC material. The focus of the study is the spin-lattice relaxation in the rotating frame, T1rho(-1), measured above the nematic-isotropic transition TNI. We show that the relaxation rate T1rho(-1)--when induced by uniform molecular translational diffusion in a spherical cavity--depends on the strength of the rotating magnetic field as T1rho(-1) proportional to omega1(-alpha) where alpha varies between 0.7 and 1, depending on the thickness of the ordered surface layer. This relaxation mechanism governs mainly the transverse spin relaxation, whereas the measurements of the frequency and temperature dependence of T1rho(-1) indicate a strong effect of slowing-down of molecular translational diffusion in contact with the polymer surface and yield the average dwell-time of molecules at the surface of the order 10(-5) s.