Effect of chain length on the adhesion behaviour of n-alkanethiol self-assembled monolayers on Au(111): An atomic force microscopy study

The effect of chain length on the adhesion behaviour of n-alkanethiols CH₃(CH₂)_nSH, wheren = 5, 6, 7, 9, 10, 11, 14 and 15 has been followed by carrying out pull-off force measurement using atomic force microscopy (AFM). The self-assembled monolayers on Au(111) surface has been characterized by reflection absorption infra-red spectroscopy (RAIRS) and contact mode AFM. It is observed that the work of adhesion is independent of thiol chain length though the standard deviation is high for short chain length thiol-based monolayers. This may be attributed to the relatively more deformable nature of the short chain thiol films due to their heterogeneity in the monolayer structure than the long chain ones. This, in turn, increases the contact area/volume between the AFM tip and the monolayer, and hence the force of adhesion. However, in the presence of water, the force of adhesion is lower than that observed in air reflecting the effects of capillary forces/polar components associated with the surface energy.     

摩擦导致的聚合物表层微观结构改变

应用大规模分子动力学方法, 模拟了锥形探头在非晶态聚合物薄膜表面的滑动摩擦过程, 研究了摩擦导致的聚合物薄膜表层微观结构改变, 以及探头与基体间黏着作用、滑动速度和分子链长度对基体表层微观结构改变的影响. 当探头与基体之间为黏着作用时, 摩擦导致基体表面滑痕区域的键取向沿滑动方向重新取向, 导致表层分子链回转半径沿滑动方向伸长, 并且这些表层微观结构的改变程度随滑动速度的减小而增大. 在摩擦导致结构改变的过程中, 链端单体和链中单体的贡献作用不同, 形成了不同的分子链拉伸变形机制. 当样本缠结度较大或探头滑动速度较小时, 相比于链中单体, 探头对链端单体的拖曳作用使更多分子链发生拉伸变形. 研究还发现, 在探头与聚合物薄膜系统中, 使薄膜表层微观结构发生改变是摩擦能量耗散的重要途径.     

Systematic study of the effect of disorder on nanotribology of self-assembled monolayers

The adhesion and friction between pairs of ordered and disordered self-assembled monolayers on SiO2 are studied using molecular dynamics. The disorder is introduced by randomly removing chains from a well ordered crystalline substrate and by attaching chains to an amorphous substrate. The adhesion force between monolayers at a given separation increases monotonically with chain length at full coverage and with coverage for fixed chain length. Friction simulations are performed at shear velocities between 0.02-2 m/s at constant applied pressures between 200 and 600 MPa. Stick-slip motion is observed at full coverage but disappears with disorder. With random defects, the friction becomes insensitive to chain length, defect density, and substrate.     

From molecular flexibility to shape, curvature and thermotropic transitions in pure surfaces

A material surface of pure constituents with a flexible molecular chain (amphiphilics) is considered; thermodynamic behaviour is studied in the chain length-temperature plane. The Hamiltonian of the system is modelled as the sum of a formation term which refers to the polymer nature of the chain, and of a fluctuation term with a specific elastic form. For closed systems the model exhibits phases with uniform curvature and conformational order/disorder or, alternatively, modulated phases; a critical chain length is found for the existence of modulated phases; the dependence of transition temperature on energy parameters is determined. A critical region is found for open systems, where conformational disorder drives spontaneous generation of curvature; this lies above a characteristic chain length and around the shape transition temperature. Received: 13 November 1996 / Revised: 9 May 1997 / Received in final form: 4 November 1997 / Accepted: 10 November 1997     

Adhesion between an elastic body and a randomly rough hard surface

I have developed a theory of adhesion between an elastic solid and a hard randomly rough substrate. The theory takes into account that partial contact may occur between the solids on all length scales. I present numerical results for the case where the substrate surface is self-affine fractal. When the fractal dimension is close to 2, complete contact typically occurs in the macro-asperity contact areas, while when the fractal dimension is larger than 2.5, the area of (apparent) contact decreases continuously when the magnification is increased. An important result is that even when the surface roughness is so high that no adhesion can be detected in a pull-off experiment, the area of real contact (when adhesion is included) may still be several times larger than when the adhesion is neglected. Since it is the area of real contact which determines the sliding friction force, the adhesion interaction may strongly affect the friction force even when no adhesion can be detected in a pull-off experiment. Received 3 April 2002     

Modification of AFM Tips for Facilitating Picking-up of Nanoparticles

The radius of atomic force microscope (AFM) tip is a key factor that influences nonspecific interactions between AFM tip and nanoparticles. Generally, a tip with larger radius contributes to a higher efficiency of picking up nanoparticles. We provide two methods for modifying the AFM tip: one is to wear a tip apex on a solid substrate and the other is to coat a tip with poly (dimethylsiloxane) (PDMS). Both the approaches can enhance the adhesion force between the tip and nanoparticles by increasing tip radius. The experimental results show that a modified tip, compared to an unmodified one, achieves six-fold efficiency improvement in the capture of targeted colloidal gold nanoparticles.     

Loss of adhesion strength of PVD Cu films on carbon substrates after heat treatment and correlated effects on the thermal interface properties

The study of coating-substrate systems consisting of a thin copper film on a flat carbon substrate is of great interest in order to get information on the interfacial behaviour of such systems. This work is focused on the mechanical adhesion strength and the correlated interfacial thermal contact resistance which are influenced by heat treatment. Using plasma-assisted pre-treatment of the carbon substrate prior to the deposition of copper coatings via physical vapor deposition (PVD), the adhesion strength between copper coatings and substrate has increased significantly, while the thermal contact resistance decreased in the as deposited state. After heat treatment at 800 °C for 1 h, considerably decreased adhesion strengths have been observed, accompanied by increased values of the thermal contact resistance.     

Modeling DNA beacons at the mesoscopic scale

We report model calculations on DNA single strands which describe the equilibrium dynamics and kinetics of hairpin formation and melting. Modeling is at the level of single bases. Strand rigidity is described in terms of simple polymer models; alternative calculations performed using the freely rotating chain and the discrete Kratky-Porod models are reported. Stem formation is modeled according to the Peyrard-Bishop-Dauxois Hamiltonian. The kinetics of opening and closing is described in terms of a diffusion-controlled motion in an effective free-energy landscape. Melting profiles, dependence of melting temperature on loop length, and kinetic time scales are in semiquantitative agreement with experimental data obtained from fluorescent DNA beacons forming poly(T) loops. Variation in strand rigidity is not sufficient to account for the large activation enthalpy of closing and the strong loop length dependence observed in hairpins forming poly(A) loops. Implications for modeling single strands of DNA or RNA are discussed.     

Indentation analysis of nano-particle using nano-contact mechanics models during nano-manipulation based on atomic force microscopy

Atomic force microscopy is applied to measure intermolecular forces and mechanical properties of materials, nano-particle manipulation, surface scanning and imaging with atomic accuracy in the nano-world. During nano-manipulation process, contact forces cause indentation in contact area between nano-particle and tip/substrate which is considerable at nano-scale and affects the nano-manipulation process. Several nano-contact mechanics models such as Hertz, Derjaguin–Muller–Toporov (DMT), Johnson–Kendall–Roberts–Sperling (JKRS), Burnham–Colton–Pollock (BCP), Maugis–Dugdale (MD), Carpick–Ogletree–Salmeron (COS), Pietrement–Troyon (PT), and Sun et al. have been applied as the continuum mechanics approaches at nano-scale. In this article, indentation depth and contact radius between tip and substrate with nano-particle for both spherical and conical tip shape during nano-manipulation process are analyzed and compared by applying theoretical, semiempirical, and empirical nano-contact mechanics models. The effects of adhesion force, as the main contrast point in different nano-contact mechanics models, on nano-manipulation analysis is investigated for different contact radius, and the critical point is discussed for mentioned models.     

Nanoindentation hardness measurements using real-shape indenters: application to extremely hard and elastic materials

We study the technique of nanoindentation hardness measurement applied to extremely hard and elastic thin films. We do the study with the aid of Hertz’s solutions for elastic contacts. The effect of different apical angles in ideally sharp conical diamond indenters is analyzed. In addition, the blunt tip shape of practical diamond indenters is discussed. The area function of the tip of real indenters is deduced from experimental nanoindentation measurements performed with these indenters on fused quartz. Triangular-base pyramidal indenters with Berkovich and cube corner geometries are considered. Theoretical hardness values applying Hertz’s and Oliver and Pharr’s methods of analysis are obtained and compared with the experimental data deduced from nanoindentation measurements performed on very hard and elastic ta-C films. The theoretical analysis shows a necessary dependence of the calculated hardness values with the apical angle of the indenter in totally elastic materials and to some extent in elastoplastic materials. Moreover, when the indenter tip is blunt or when there are inaccuracies in the measured area function of the indenter tip, hardness values decrease for very small penetration depths. Besides, in these films, because of their very small thickness, measured hardness values also decrease for measurements with penetration depths larger than a fraction of film thickness, due to the effects of the softer substrate. Received: 13 June 2000 / Accepted: 21 June 2000 / Published online: 5 October 2000     

纳米接触过程中黏着规律的变化

本文应用大规模分子动力学方法, 模拟了两种具有不同粗糙形貌的、刚性球形探头与弹性平面基体之间的纳米尺度接触, 计算了探头与基体之间的拉离力和黏着功, 研究了接触过程中界面黏着力随载荷的变化规律, 分析了接触界面原子的法向应力分布. 研究发现, 原子级光滑接触的黏着力随着载荷的增大而线性增大, 而原子级粗糙接触的黏着力-载荷曲线分为以不同斜率增长的两个阶段. 相比于原子级光滑探头, 原子级粗糙探头与基体之间具有较小的拉离力和黏着功, 却在接触过程中形成了较大的黏着力. 因此, 拉离力和黏着功不能表征出纳米接触过程中原子吸引作用对界面法向力的贡献大小.     

Force-extension behavior of folding polymers

The elastic response of flexible polymers made of elements which can be either folded or unfolded, having different lengths in these two states, is discussed. These situations are common for biopolymers as a result of folding interactions intrinsic to the monomers, or as a result of binding of other smaller molecules along the polymer length. Using simple flexible-chain models, we show that even when the energy ε associated with maintaining the folded state is comparable to k _B T, the elastic response of such a chain can mimic usual polymer linear elasticity, but with a force scale enhanced above that expected from the flexibility of the chain backbone. We discuss recent experiments on single-stranded DNA, chromatin fiber and double-stranded DNA with proteins weakly absorbed along its length which show this effect. Effects of polymer semiflexiblity and torsional stiffness relevant to experiments on proteins binding to dsDNA are analyzed. We finally discuss the competition between electrostatic self-repulsion and folding interactions responsible for the complex elastic response of single-stranded DNA. Received 7 August 2002 and Received in final form 7 March 2003 / Published online: 15 April 2003 RID="a" ID="a"e-mail: jmarko@uic.edu     

The influence of structure of the interface and interphase on paint adhesion

It has been demonstrated earlier that significant adhesion enhancement to chemically inert polyolefins can be attained through surface grafted connector molecules reactive with oxidized substrate surface. The effectiveness of adhesion improvement through such tethered interfaces was shown to depend on the mode of interaction with the adjacent medium: interpenetration or chemical reaction, as well as surface density and length of grafted molecules. We have frequently observed that some systems, such as in painted products, fail through the delamination of the coating from the substrate surface at the stress levels well below the anticipated load-bearing capacity of the tethered interface. Two interim hypotheses have been formulated to explain the observed phenomenon: (i) The chain scission in surface oxidized polyolefins takes place not only in the uppermost polymer surface, but may propagate into the sub-surface region, thus creating a weak boundary layer which fails cohesively through its bulk, (ii) In order to increase the load-bearing capacity of the interphase, the sub-surface region of the substrate needs to be reinforced by short-chain molecules penetrating into and subsequently providing effective crosslinks between individual fragments of excessively oxidized and hence, weaker sub-surface part of the interphase. In this paper we verify the above hypotheses. The oxidized sub-surface layer reinforced by polyethyleneimine becomes an integral part of the effective interphase in addition to the tethered interface and the interpenetrated network of connector molecules and the paint.     

采用阶梯形弹性基底的磁致伸缩/压电复合结构磁电响应研究

利用阶梯形变幅杆的应变放大作用,构造了磁致伸缩/阶梯形弹性基底/压电复合结构. 采用等效电路法分析了沿长度方向振动复合结构的一阶磁电响应. 计算了Terfenol-D/阶梯形铍青铜基底/PZT-5H复合结构的磁电响应,并与实际结构的磁电响应进行了比较,由于理论分析中忽略了胶层产生的损耗,理论值和实验结果的变化规律相似,但是谐振频率点和磁电电压转换系数有一定的差异. 同时比较了阶梯形基底和等截面杆基底复合结构,分析表明前者具有更高的磁电电压转换系数. 研究了阶梯形弹性基底长度比及层厚比对复合结构纵振动一阶模 关键词： 磁电效应 磁致伸缩/压电复合结构 磁电响应     

Electrostatic forces in micromanipulations: Review of analytical models and simulations including roughness

Manipulations by contact of objects between 1 m and 1 mm are often disturbed by adhesion between the manipulated object and the gripper. Electrostatic forces are among the phenomena responsible for this adhesive effect. Analytical models have been developed in the literature to predict the electrostatic forces. Most models are developed within the framework of scanning probe microscopy, i.e. for a contact between a conducting tip and a metallic surface. Models are reviewed in this work and compared with our own simulations using finite elements modeling. The results show a good correlation. The main advantage of our simulations lies in the fact that they can integrate roughness parameters. For this purpose, a fractal representation of the surface topography was chosen through the use of the Weierstrass-Mandelbrot function. Comparisons with experimental benchmarks from the literature show very good correlation between experimental results and simulations. It demonstrates the importance of surface topography on electrostatic forces at very close separation distances.     

Adhesion between elastic bodies with randomly rough surfaces

I have developed a theory of adhesion between an elastic solid and a hard randomly rough substrate. The theory takes into account the fact that partial contact may occur between the solids on all length scales. I present numerical results for the case where the substrate surface is self-affine fractal. When the fractal dimension is close to 2, complete contact typically occurs in the macroasperity contact areas. For a fractal dimension larger than 2.5, the area of (apparent) contact decreases continuously when the magnification is increased.     

表面黏附导致的接触行为转变

应用大规模分子动力学方法, 模拟了具有不同原子级粗糙形貌的两种刚性球形探头与弹性平面基体的黏附接触行为. 研究了载荷与真实接触面积、接触界面排斥力与真实接触面积, 以及黏附力与真实接触面积之间的关系. 分子模拟得到的载荷与真实接触面积的关系, 与连续力学接触理论预测很好地定性一致. 无论是原子级光滑探头还是粗糙探头, 黏附接触下的排斥力与真实接触面积的关系, 都与无黏附接触时的规律相一致, 即黏附力对接触行为的影响作用, 可以等效为附加在真实外载荷基础上的虚拟载荷, 将对黏附接触行为的分析转变为无黏附接触分析. 两种探头的黏附力随真实接触面积都呈幂函数形式的增长, 但是, 原子级光滑探头的幂指数大于1, 而原子级粗糙探头的幂指数小于1. 关键词： 接触行为 表面黏附 分子动力学模拟     

On the validity of Hertz contact law for granular material acoustics

We discuss the acoustical behavior of a 1D model of granular medium, which is a chain of identical spherical beads. In this geometry, we are able to test quantitatively alternative models to the Hertz theory of contact between elastic solids. We compare the predictions of the different models to experimental results that concern linear sound wave propagation in the chain submitted to a static force, and nonlinear solitary wave propagation in an unconstrained chain. We use elastic, elastic-plastic and brittle materials, the beads roughness extends on one order of magnitude, and we also use oxidized metallic beads. We demonstrate experimentally that at low static forces, for all types of beads, the linear acoustic waves propagate in the system as predicted by Hertz's theory. At larger forces, after onset of permanent plastic deformation at the contacts, the brass beads exhibit non Hertzian behavior, and hysteresis. Except in the case of brass beads, the nonlinear waves follow the predictions of Hertz theory. Revised: 28 May 1998 / Accepted: 27 July 1998     

The segregation of poly(styrene-b-isoprene) diblock copolymers to the surface of a polystyrene melt: the effect of the ratio of block lengths

The effect of the ratio of block lengths on the interfacial partitioning of poly(styrene-block-1,4 isoprene) diblock copolymers from their mixtures with polystyrene homopolymer melt is investigated utilizing a series of copolymers with almost constant molecular weight but different compositions. The concentration profile of the copolymer is measured directly using the nuclear reaction analysis technique; a segregation of the diblock is found at both the air/polymer surface, due to the lower surface energy of polyisoprene, and at the substrate/polymer interface. No significant effect of the block length ratio on the free-surface excess was observed. The block molecular weights have apparently led to dangling chain conformations in the non-overlapping mushroom and in the overlapping mushroom regimes whereas the brush regime was not accessible; no indications of a real border between the two former regimes was found. Received: 20 July 1998 / Received in final form and Accepted: 11 September 1998     

Elastic modulus-density relationship for amorphous boron suboxide thin films

Boron suboxide thin films have been deposited on Si(100) substrates by reactive RF magnetron sputtering of a sintered B target in an Ar/O₂ atmosphere. Elastic recoil detection analysis was applied to determine the film composition and density. Film structure was studied by X-ray diffraction and transmission electron microscopy. The elastic modulus, measured by nanoindentation, was found to decrease as the film density decreased. The relationship was affected by tuning the negative substrate bias potential and the substrate temperature during film growth. A decrease in film density, by a factor of 1.55, caused an elastic modulus reduction by a factor of 4.5, most likely due to formation of nano-pores containing Ar. It appears evident that the large scattering in the published data on elastic properties of films with identical chemical composition can readily be understood by density variations. These results are important for understanding the elastic properties of boron suboxide, but may also be qualitatively relevant for other B-based material systems. Received: 22 February 2002 / Accepted: 11 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +46-13/288-918, E-mail: denmu@ifm.liu.se