Measuring Energies at the Nanometer-Scale of Molecular Organic Materials with an Atomic Force Microscope: TTF-TCNQ as a Case Study

The elastic response of molecular organic materials to external mechanical nanoindentations in the nano- and low micronewton force range can be characterized using ultrasharp cantilever tips of an Atomic Force Microscope (AFM). Because clear distinction between elastic and plastic deformation is achieved, the maximal accumulated elastic energy can be directly determined from the force vs. penetration curves, giving an estimate of the characteristic energies of the materials.     

A method to quantitatively measure the elastic modulus of materials in nanometer scale using atomic force microscopy

A method is proposed for quantitatively measuring the elastic modulus of materials using atomic force microscopy (AFM) nanoindentation. In this method, the cantilever deformation and the tip-sample interaction during the early loading portion are treated as two springs in series, and based on Sneddon's elastic contact solution, a new cantilever-tip property α is proposed which, together with the cantilever sensitivity A, can be measured from AFM tests on two reference materials with known elastic moduli. The measured α and A values specific to the tip and machine used can then be employed to accurately measure the elastic modulus of a third sample, assuming that the tip does not get significantly plastically deformed during the calibration procedure. AFM nanoindentation tests were performed on polypropylene (PP), fused quartz and acrylic samples to verify the validity of the proposed method. The cantilever-tip property and the cantilever sensitivity measured on PP and fused quartz were 0.514?GPa and 51.99?nm?nA(-1), respectively. Using these measured quantities, the elastic modulus of acrylic was measured to be 3.24?GPa, which agrees well with the value measured using conventional depth-sensing indentation in a commercial nanoindenter.     

From hollow shells to artificial cells: biointerface engineering on polyelectrolyte capsules

Biomimetic composites can be fabricated by coating hollow polyelectrolyte capsules with biological interfaces such as a phospholipid membrane and proteins. Polyelectrolyte capsules have been templated applying the Layer-by-Layer technique of polyelectrolyte assembled on decomposable cores, which are destroyed after the assembly of the polyelectrolyte multilayer. Phospholipid vesicles of 200-300 nm size are spreaded on the capsule wall forming a continuous lipid membrane. Further functionalisation of the outer capsule wall can be achieved with fused virions and recrystallised S-layers. Compartimentation of the capsule interior with lipid vesicles has been possible by using a solvent exchange method. The functionalisation of the outer capsule surface with biomolecules, together with the creation of internal compartments in the capsule, open new nanobiotechnological challenges towards the fabrication of artificial cells.     

Characterization of polysulfone and polysulfone/vanillin microcapsules by 1H NMR spectroscopy, solid-state 13C CP/MAS-NMR spectroscopy, and N2 adsorption-desorption analyses

Textile detergent and softener industries have incorporated perfume microencapsulation technology to improve their products. Perfume encapsulation allows perfume protection until use and provides a long-lasting fragrance release. But, certain industrial microcapsules show low encapsulation capacity and low material stability. Polysulfone capsules have been already proposed to solve these drawbacks. Among them, PSf/Vanillin capsules were considered as a desirable system. They present both good material stability and high encapsulation capacity. However, several factors such as the final location of the perfume in the polymeric matrix, the aggregation state that it has in the capsule and its interaction with the capsule components have not been studied yet. These factors can provide vast information about the capsule performance and its improvement. With the aim to characterize these parameters, the physical and chemical properties of PSf/Vanillin capsules have been investigated by nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and N(2) adsorption-desorption measurements. AFM micrograph and N(2) isotherms confirm that the presence of vanillin modify the physical structure of PSf/Vanillin microcapsules as it is trapped in the capsule porosity. NMR results show that vanillin is present in solid state in PSf/Vanillin microcapsules.     

Redox-controlled molecular permeability of composite-wall microcapsules

Many smart materials in bioengineering, nanotechnology and medicine allow the storage and release of encapsulated drugs on demand at a specific location by an external stimulus. Owing to their versatility in material selection, polyelectrolyte multilayers are very promising systems in the development of microencapsulation technologies with permeation control governed by variations in the environmental conditions. Here, organometallic polyelectrolyte multilayer capsules, composed of polyanions and polycations of poly(ferrocenylsilane) (PFS), are introduced. Their preparation involved layer-by-layer self-assembly onto colloidal templates followed by core removal. PFS polyelectrolytes feature redox-active ferrocene units in the main chain. Incorporation of PFS into the capsule walls allowed us to explore the effects of a new stimulus, that is, changing the redox state, on capsule wall permeability. The permeability of these capsules could be sensitively tuned via chemical oxidation, resulting in a fast capsule expansion accompanied by a drastic permeability increase in response to a very small trigger. The substantial swelling could be suppressed by the application of an additional coating bearing common redox-inert species of poly(styrene sulfonate) (PSS(-)) and poly(allylamine hydrochloride) (PAH(+)) on the outer wall of the capsules. Hence, we obtained a unique capsule system with redox-controlled permeability and swellability with a high application potential in materials as well as in bioscience.     

CYCLIC BEHAVIOUR AND ROOM TEMPERATURE MICROMECHANISMS OF 3Y-TZP CERAMICS AT SUBMICRON AND NANOCRYSTALLINE LEVELS

Abstract— The cyclic behaviour and micromechanisms of 3Y-TZP ceramics were investigated at a stress ratio, R , of 0.1 and a frequency of 0.1 Hz at room temperature for both nanocrystalline (100nm) and submicron polycrystalline (0.35μm) 3Y-TZP ceramics. The nanocrystalline material displayed cyclic softening, but the submicron polycrystalline material displayed cyclic hardening. The cyclic hardening resulted mainly from saturation of tetragonal to monoclinic phase transformation which induced a higher internal stress in the material; the cyclic softening resulted partly from the formation of microcracks along the grain boundary of the tetragonal phase.
Superplastic deformation was first found by the Scanning Electron Microscope and the Atomic Force Microscope (AFM) in some micro-areas of the fatigue fracture surface of the nanocrystalline material. Furthermore it was observed by AFM that there were a large number of slip lines and an early stage for the formation of an extrusion on the side edge of the fracture. From this it was deduced that the micromechanism of local superplasticity resulted from the slip motion of dislocation.     

Accuracy of the spring constant of atomic force microscopy cantilevers by finite element method

Atomic force microscopy (AFM) probe with different functions can be used to measure the bonding force between atoms or molecules. In order to have accurate results, AFM cantilevers must be calibrated precisely before use. The AFM cantilever's spring constant is usually provided by the manufacturer, and it is calculated from simple equations or some other calibration methods. The spring constant may have some uncertainty, which may cause large errors in force measurement. In this paper, finite element analysis was used to obtain the deformation behavior of the AFM cantilever and to calculate its spring constant. The influence of prestress, ignored by other methods, is discussed in this paper. The variations of Young's modulus, Poisson's ratio, cantilever geometries, tilt angle, and the influence of image tip mass were evaluated to find their effects on the cantilever's characteristics. The results were compared with those obtained from other methods.     

端部受撞击作用弹塑性悬臂曲梁的大挠度动力响应

考虑弹性运动与曲梁运动的相互耦合，基于大变形平衡微分方程并利用有限差分离散分析，研究了端部受撞击作用弹-塑性悬臂曲梁的大挠度动力响应。通过对响直各时刻弯矩分布规律的细致分析，阐明悬臂曲梁动力响应过程中，弹性效应对变形机制和响应模式的重要影响。与刚塑性分析所假定两相变形模式比较，弹塑性响应分析肯定了刚塑性分析所假定变形模式的主要特征，合理解释了撞击发生后，曲梁局部区段所产生的反向弯曲变形以及在曲梁中部出现的高曲率现象。     

Mechanical property of lipid-coated polyelectrolyte microcapsules

The deformations of lipid coated polyelectrolyte capsules induced by osmotic pressure were determined in poly(styrene sulfonate, sodium salt) (PSS) solution by making use of the fact that PSS molecules with a molecular weight 70000 will not penetrate into the capsules. At a critical osmotic pressure the initial spherical capsules changed their shape and became an invagination. The measurements of single particle light scattering provided the wall thickness of the lipid-coated capsules with 25.6 nm while the thickness for pure polyelectrolyte capsules in solution is about 21.6 nm, indicating that the coating lipid layer has about 4 nm thickness. It demonstrates that DMPA forms a bilayer on the surface of polyelectrolyte capsules. With these data, that the elasticity coefficient of the lipid-coated capsules is about 426 Mpa can be obtained.     

上浆剂对国产T700级碳纤维复合材料界面性能的影响

采用扫描电镜(SEM)、原子力显微镜(AFM)、X射线光电子能谱(XPS)等测试方法表征了上浆/未上浆国产T700级(MT700)碳纤维的表面特性,并通过单丝断裂实验测试了单丝复合体系微观界面剪切强度(IFSS),在此基础上研究了碳纤维表面特性对单丝复合体系微观界面性能及其耐湿热性能的影响.研究表明:MT700碳纤维表面上浆剂改善了纤维/基体微观界面强度及其耐湿热性能;湿热环境对复合材料的微观界面性能影响显著,尤其是造成纤维/基体间的化学键合作用破坏,去湿后部分界面性能可恢复.     

Determining Mechanical Properties of Carbon Microcoils Using Lateral Force Microscopy

Mechanical properties of amorphous carbon microcoil (CMC) synthesized by thermal chemical vapor deposition method were examined in compression and tension tests, using the lateral force mode of atomic force microscope (AFM). The AFM cantilever tip was manipulated by a piezoelectric scanner to contact, pull, and push an individual CMC. The lateral force that was exerted by the CMC deformation causes the twist of the AFM cantilever. It was monitored by the laser and photodetector of the AFM during the experiments. A linear response of the CMC was observed in the range of 25 nm to 5 mum of tension experiments. The results show that the spring constant of the CMC is reasonably proportional to the coil number. The shear modulus of the amorphous CMC is estimated to be 3 plusmn 0.2 GPa. The proposed method is promising to manipulate the compression and tension of the CMC and to measure the lateral force exerted in an ambient environment.     

Atomic force microscopy tip torsion contribution to the measurement of nanomechanical properties

The nanomechanical properties of polymethyl methacrylate and indium phosphide were measured with an atomic force microscope and a nanoindentation system. The elastic moduli measured with the atomic force microscope are in good agreement with the values obtained with the nanoindentation system. The hardness is shown to be affected by the tip radius used in our experiments. The cantilever vertical and lateral movements were independently analyzed during nanoindentation, and the tip torsion can be attributed to a change from elastic to plastic deformation regimes of materials during force microscopy nanoindentation. An analysis of the lateral movement of the laser beam associated with the cantilever torsion was used to determine the material yield stress.     

Determination of mechanical properties of electroplated Ni thin film using the resonance method

This paper addresses a relatively simple method of measuring the mechanical properties such as Young's modulus and residual stress of electroplated Ni thin film using the resonance method of Atomic Force Microscope. Thin layer of nickel to be measured is electroplated onto the tip side of AFM silicon cantilever and plating thicknesses were measured at the end of each plating step. The measured Young's modulus of nickel at the end of each plating step ranged from 148.04 GPa to 159.90 GPa with the maximum standard deviation of 3.47. The end deflection of electroplated AFM cantilever is also measured as a function of the plated Ni thickness, which is converted into the film stress by appropriate mechanics.     

Experimental study on the dynamic behavior of TiNi cantilever beams with rectangular cross-section under transversal impact

The experimental investigation of TiNi alloy cantilever in the PE state and R-SME state, respectively, was conducted under transversal impact by using a modified Hopkinson bar apparatus. For comparison, the impact response of A3 steel cantilevers with the same geometry was also studied. The results show that at an early stage the elastic flexible waves dominate the wave response of the beam. After about 1 ms the dynamic structural response will be the main response. Under impact the “phase transformation hinge (TH)”, which differs from the conventional plastic hinge (PH), may form and undertake the main deformation and energy absorption in a cantilever. The impact position has a great influence on the location, time and number of the formation of TH, hence the response mode of a cantilever. After impact there is no residual deformation for a PE cantilever, there is a small residual deformation for an R-SME cantilever due to the R transition and large residual deformation for steel cantilevers due to the plasticity. The energy absorption efficiency of cantilevers for different materials and impact conditions are discussed.     

Fabrication of Au/SiO2 Nanocomposite Films by Self-Assembly Multilayer Method

Gold colloid was prepared by chemical reduction of hydrogen tetrachloroaurate, polyelectrolyte/gold nanoparticle/silica nanoparticie composite films were fabricated via an electrostatic self-assembly multilayer method, and composite films of gold nanoparticle dispersed in silica matrix were formed by heat-treating the polyelectrolyte/gold nanoparticle/silica nanoparticle composite films to eliminate the polyelectrolyte. The obtained composite films were investigated with UV-vis, TEM, AFM and XRD. The results show that the self-assembly multilayer method is a promising process to produce composite films of gold nanoparticle-dispersed in organic and/or inorganic matrixes.     

Nano-scratching and nano-machining in different environments on Cr2N/Cu multilayer thin films

Five nanostructured Cr₂N/Cu multilayer coatings were deposited by a bipolar asymmetric reactive pulsed DC magnetron sputtering system, and various bilayer periods (Λ) were achieved by controlling the holding time of Si substrates in the plasma of Cr or Cu. The hardness and elastic modulus of multilayer coatings were investigated by means of a nanoindenter. Nano-scratch and nano machining experiments on multilayered coatings were conducted using atomic force microscopy (AFM) in air and DI-water, respectively. According to the groove depth, width, and coefficient of friction (COF) obtained from nano-scratch tests, influences of scratch cycle numbers and bilayer periods on the scratchability of Cr₂N/Cu multilayered thin films were examined. It was observed that after nano-scratch experiments in air and water, the COF values and the amount of removed material increased with increasing bilayer period. After nano-machining tests in air and water, different types of the cutting chip pile-ups were observed. In this work, the surface tribological properties and machinability of Cr₂N/Cu multilayered thin films when using an AFM are discussed.     

Study of the low stress plasticity in single-crystal MgO by nanoindentation and atomic force microscopy

Berkovich nanoindentations have been performed at ambient temperature with a new apparatus on (001) cleaved surfaces of single-crystal Magnesium Oxide (MgO). Rosette slip lines pattern has been observed at a nanometric scale by Atomic Force Microscope. Moreover, the load-displacement curves present particular features such as pop-in, which has been linked to the AFM surface topography observations. Finally, we show that the combination of a new nanoindentation apparatus and an Atomic Force Microscope allows to study the very early stages of the plastic deformation during a nanoindentation in terms of individual dislocations.     

一种消除AFM中悬臂梁横向扭转串扰误差的修正技术

串扰效应始终存在于原子力显微镜(AFM)的测量过程中,并影响其测量精度.在对串扰效应的产生机理进行分析,并建立了悬臂梁形变与光斑位置检测器(PSPD)输出信号之间的数学关系的基础上,提出了一种可消除横向扭转串扰影响的修正方法.在该方法中AFM系统可由输出信号直接获得悬臂梁的实际形变量,进而获得原子间作用力的实际值,并通过保持作用力的恒定对样品进行测量.该方法可有效地将悬臂梁扭转导致的纵向信号的变化从系统测得的纵向信号中剔除出去.仿真结果表明,在恒力接触模式下,串扰效应严重影响测量结果,导致测量误差,且针尖.样品夹角导致的串扰效应比摩擦力导致的串扰效应更严重.为验证本文方法消除串扰效应的效果,在应用该修正方法前后分别对标准梯形样品进行测量.实验对比结果表明,在普通恒力接触模式下的样品表面最大测量误差范围为21.2 nm～32.0 nm;对串扰效应进行修正后,最大测量误差范围降低至5.5 nm～10.2 nm.这表明该方法可有效降低AFM中串扰效应导致的测量误差,提高其测量精度.     

移动分布荷载下层状粘弹性体系的动力响应分析

以粘弹性Burgers模型模拟沥青面层,建立了路面结构层状粘弹性体系模型。利用积分变换和传递矩阵法,并结合广义Duhamel积分,推导出了移动分布荷载作用下层状粘弹性体系动力响应的解析解。利用样条插值函数开发了计算奇异、振荡函数多重无穷积分的计算程序,完成了动力响应从波数-频率域到时间-空间域的转化,与已有文献数据和有限元结果进行了比较,显示出了较好的一致性。结合算例分析了移动分布荷载作用下层状粘弹性体系的振动特性。结果表明,粘弹性解大于弹性解,Burgers模型能反映沥青路面变形的滞后现象,层状粘弹性体系的垂向位移随行车速度和Burgers模型材料参数的增加而减小。     

The effects of asymmetrical cold rolling on kinetics,grain size and texture in IF steels

Asymmetrical rolling is a promising way to achieve high rolling reductions and potentially grain refinement. However in steels the effect of asymmetrical rolling is not thoroughly quantified. In this paper the impact of cold asymmetrical rolling obtained by changing the roll velocity ratio (from 1.1 to 1.45) on the deformation and recrystallization features has been finely investigated by Electron Back-Scattering Diffraction in a Scanning Electron Microscope. In the investigated conditions (with low thickness reduction), it is found that asymmetrical rolling induces grain refinement and more homogeneous gamma fiber texture.