Adhesion and friction of PDMS networks: molecular weight effects

The objective of this work is to find relations between adherence and friction behaviors of elastomer networks. The chosen approach is based on the parallel study of the initial molecular weight (i.e., the degree of cross-linking) dependence of both adherence and friction. The polymers used are cross-linked polydimethylsiloxane (PDMS) and the substrate is a smooth glass plate. The experimental procedure uses both friction (pin on disk tribometer) and adhesion (tack test) measurements, associated with surface analysis and mechanical and rheological characterizations. Tack results show that high molecular weight PDMS exhibits the greater adherence energy. This can be explained by the role of both chain length and free and pendant chains: more numerous and longer free chains favor the substrate wetting (at a molecular scale) and increases the energy dissipation during separation (extraction and reptation mechanisms). However, friction results indicate a higher friction resistance for low molecular weight PDMS. This result could be quite surprising. An explanation based on interfacial sliding properties of free and pendant chains can be proposed. Elsewhere, for the lower molecular weight polymer, elastic contact present during friction is able to act as a forced wetting, constraining the network and consequently leading to a greater energy dissipation.     

Molecular simulation studies of nanoscale friction between phosphorylcholine self-assembled monolayer surfaces: correlation between surface hydration and friction

We performed all-atom molecular dynamics simulations to study the friction between surfaces covered with two phosphorylcholine self-assembled monolayers (PC-SAM) under shear. PC-SAM surfaces with a sqrt7 X sqrt7R19 degrees lattice structure and a parallel arrangement of the head groups were used as model zwitterionic surfaces. They provide a full representation of the zwitterionic nature of phospholipid surfaces, which are believed to play an important role in the lubrication of biological joints such as knees and hips. The surfaces were immersed in aqueous solutions and kept in contact with two regions of bulk water. Sodium chloride and potassium chloride solutions at various concentrations were employed to study the effects of the presence of ions on friction. The results show a strong relationship between surface hydration and friction. Higher ionic concentrations or ions with shorter Debye lengths cause a larger disruption to the hydration around the zwitterionic surfaces, leading to larger friction forces. In addition, the results show that under nanoscale confinement, the friction coefficients of PC-SAM surfaces in pure water are directly proportional to both shear velocity and surface separation distance. These results are comparable to previously published experimental studies.     

Chemical modification of fluorinated self-assembled monolayer surfaces by low energy reactive ion bombardment

Reactive collisions of low energy (<100-eV) mass-selected ions are used to chemically modify fluorinated self-assembled monolayer surfaces comprised of alkanethiolate chains CF₃(CF₂)₁₁(CH₂)₂S— bound to Au. Typical experiments were done by using 1-nA/cm² beams and submonolayer doses of reactant ions. Characterization of the modified surface was achieved by in situ chemical sputtering (60-eV Xe^+·) and by independent high mass resolution time-of-flight-secondary ionization mass spectrometry (TOF-SIMS) (15–25-keV, Ga⁺) experiments. Treatment with Si³⁵C1 ₄ ^+· produced a surface from which Xe⁺ sputtering liberated CF₂ ³⁵C1⁺ ions, which suggested Cl-for-F halogen exchange at the surface. Isotopic labeling studies that used Si³⁵Cl₂ ³⁷Cl ₂ ^+· ; and experiments with bromine-containing and iodine-containing projectiles, confirmed this reaction. High mass resolution TOF-SIMS spectra, as well as high spatial resolution images, provided further evidence as to the existence of halogen-exchanged species at the bombarded surface. Analogous Cl-for-F halogen substitution was observed in a model gas-phase reaction. The ion-surface reaction is suggested to proceed through an intermediate fluoronium ion in which the projectile is bonded to the target molecule. The most significant conclusion of the study is that selective chemical modification of monolayer surfaces can be achieved by using reactive ion beams, which lead to new covalent bonds at the surface and in the scattered ions.     

Selective growth of a less stable polymorph of 2-iodo-4-nitroaniline on a self-assembled monolayer template

Orthorhombic and triclinic crystals of 2-iodo-4-nitroaniline (INA) grow concomitantly from supersaturated ethanol solutions, but the less stable orthorhombic phase can be selectively grown on 3'-X-4-mercaptobiphenyl (X = NO(2), I) self-assembled monolayer templates.     

Adhesion and friction properties of molecularly thin perfluoropolyether liquid films on solid surface

The adhesion and friction properties of molecularly thin perfluoropolyether (PFPE) lubricant films dip-coated on a diamond-like carbon (DLC) overcoat of magnetic disks were studied using a pin-on-disk-type micro-tribotester that we developed. The load and friction forces were simultaneously measured on a rotating disk surface under an increasing/decreasing load cycle and slow sliding conditions. Experiments were performed using two types of PFPE lubricants: Fomblin Z-tetraol2000S with functional end-groups and Fomblin Z-03 without any end-group. The curves of the friction force as a function of the applied load agree with the curves estimated using the Johnson-Kendall-Roberts (JKR) model. The friction forces on the Z-03 films having different thicknesses were not found to decrease drastically; however, the friction forces on the Z-tetraol film were found to decrease drastically when the film thickness is more than ~1.2 nm. This drastic change in the case of the Z-tetraol film is estimated to be affected by the coverage of the lubricant film.     

Realization of monolayer levels of surface oxidation of nickel by anodization at low temperatures

In order to examine whether monolayer or sub-monolayer extents of surface oxidation can be realized experimentally at Ni prior to onset of bulk-phase oxide formation (as they can for example at Pt, Ru or Au already at room temperature), cyclic voltammetric experiments down to low temperature (−90° C) have been conducted on Ni in solutions of NaOH in 80 mol% methanol with water. The cyclic voltammograms for the first stage of Ni oxidation to α-Ni(OH)₂, and its reduction, show that extents of surface oxidation down to an equivalent monolayer, or less, of Ni(OH)₂ can be realized at sufficiently low temperatures. However, even at these low levels of oxidation of the metal, irreversibility between the processes of Ni oxide formation and reduction is maintained in a way characteristic of the behavior of three-dimensional oxide films. It therefore appears that even at low levels of surface oxidation of Ni which are attainable at low temperature, the oxidation mechanism involves nucleation and growth of the oxide in islands rather than an initial surface-chemical process of OH or O array formation, as at Pt or Au. However, no indications of a dissolution-and precipitation type of oxide formation process, which would involve mass-transport in solution, are given by the present results obtained from experiments in dilute alkali at low temperatures, and at the rotating Ni disc electrode.     

Creation of unique supramolecular nanoarchitectures utilizing natural polysaccharide as a one-dimensional host

We recently revealed that β-1,3-glucans act as unique natural nanotubes, which can accept functional polymers and molecular assemblies in an induced-fit manner. A variety of individual conjugated polymers or molecular assemblies can be incorporated into the one-dimensional hollow constructed by the helical superstructure of β-1,3-glucans to create water-soluble one-dimensional nanocomposites. The advantageous point of the present hosting system is that the selective modification of β-1,3-glucans leads to the creation of various functional one-dimensional nanocomposites in a supramolecular manner. Furthermore, the composites with functional surfaces can act as one-dimensional building blocks toward further hierarchical self-assembles, leading to the creation of two- or three-dimensional nanoarchitectures, which are applicable for fundamental nanomaterials.     

Shaken, not stirred: collapsing a peptoid monolayer to produce free-floating, stable nanosheets

Two-dimensional nanomaterials play a critical role in biology (e.g., lipid bilayers) and electronics (e.g., graphene) but are difficult to directly synthesize with a high level of precision. Peptoid nanosheet bilayers are a versatile synthetic platform for constructing multifunctional, precisely ordered two-dimensional nanostructures. Here we show that nanosheet formation occurs through an unusual monolayer intermediate at the air-water interface. Lateral compression of a self-assembled peptoid monolayer beyond a critical collapse pressure results in the irreversible production of nanosheets. An unusual thermodynamic cycle is employed on a preparative scale, where mechanical energy is used to buckle an intermediate monolayer into a more stable nanosheet. Detailed physical studies of the monolayer-compression mechanism revealed a simple preparative technique to produce nanosheets in 95% overall yield by cyclical monolayer compressions in a rotating closed vial. Compression of monolayers into stable, free-floating products may be a general and preparative approach to access 2D nanomaterials.     

Adhesion and friction studies of Au nanoparticle‐textured surfaces with colloidal tips

Surface roughness plays an important role in affecting the adhesive force and friction force in microelectromechanical systems (MEMS)/nanoelectromechanical systems (NEMS). One effective approach of reducing adhesion and friction of contacting interfaces is to create textured surface, which is especially beneficial for MEMS'/NEMS' production yield and product reliability. In this article, we present a convenient method to fabricate the nano‐textured surfaces by self‐assembling Au nanoparticles (NPs) on the silicon (100) surfaces. The nanoparticle‐textured surfaces (NPTS) with different packing density and texture height were prepared by controlling the assembling time and the size of Au NPs. The morphologies and chemical states of NPTS were characterized by atomic force microscope (AFM), field emission scanning electron microscope, and XPS. The adhesion and friction on the NPTS were studied by AFM with colloidal tip. The results show that the nano‐textured surfaces have effectively reduced adhesive force and friction force compared with the 3‐aminopropyl trimethoxysilane self‐assembled monolayer surfaces. The lowered adhesion and friction were attributed to the reduced real area of contact between NPTS and colloidal tip. The adhesion and friction of the NPTS are varying with the texture packing density and dependent on both the texture height and asperities spacing, which are related to the size and coverage ratio of NPs on surfaces. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of low levels of cadmium ions by the under potential deposition on a self-assembled monolayer on gold electrode

Despite the advantages of simplicity and high-throughput detection that matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has over other methods, quantitative analysis of low-molecular-weight analyte is hampered by interference from matrix-derived background noise and signal fluctuation due to the inhomogeneous MALDI sample surface. Taking advantage of improved sample homogeneity through matrix-conjugated magnetic nanoparticles (matrix@MNP) and the seed-layer method, we report a new strategy for the rapid identification and quantification of drugs in urine samples, using morphine and 7-aminoflunitrazepam (7-aminoFM2) as model compounds. To our knowledge, this is the first attempt using the seed-layer method for small molecule analysis. By applying the proposed seed-layer method, which was specifically optimized for the 2,5-dihydroxybenzoic acid@MNP (DHB@MNP) matrix, homogeneous sample crystallization examined by microscopy analysis was obtained that generated reproducible MALDI signals (RSD<10.0%). For urine sample analysis, simple liquid-liquid extraction as a sample pretreatment step effectively reduced the ion suppression effect caused by the endogenous components in urine; good recoveries (82-90%) were obtained with a small ion suppression effect (<14% of signal decrease). This newly developed method demonstrated good quantitation linearity over a range of 50-2000 ng mL(-1) (R(2)>0.996) with reduced signal variation (RSD<10.0%). The detection limit is 30 ng mL(-1) with good precision (intra-day, 2.0-9.3%; inter-day, 5.0-10.0%) and accuracy (intra-day, 95.0-106.0%; inter-day, 103.0-115.5%). The nanoparticle-assisted MALDI-TOF MS combined with seed-layer surface preparation provides a rapid, efficient and accurate platform for the quantification of small molecules in urine samples.     

Chemical stability of nonwetting, low adhesion self-assembled monolayer films formed by perfluoroalkylsilanization of copper

A self-assembled monolayer (SAM) has been produced by reaction of 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) with an oxidized copper (Cu) substrate and investigated by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, and contact angle measurement. FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. The perfluoroalkyl SAM on Cu is found to be extremely hydrophobic, yielding sessile drop static contact angles of more than 130 degrees for pure water and a "surface energy" (which is proportional to the Zisman critical surface tension for a Cu surface with 0 rms roughness) of 14.5 mJm2(nMm). Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH=12, 60 degrees C) solutions for at least 30 min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70 min at 60 degrees C or 50 min at 80 degrees C. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for antiwetting, low adhesion surfaces or dropwise condensation on heat exchange surfaces.     

Competition of natural polyamines with dimethylsilyl analogues and monovalent cations in presence of a charged dipalmitoylphosphatidylglycerol monolayer

The interaction at the air/water interface of dipalmitoylphosphatidylglycerol (DPPG) with natural and dimethylsilyl polyamines are investigated first in the presence of NaCl in the subphase. Next, experiments are performed to study the competition between natural polyamines and dimethylsilyl analogues. The results obtained by surface pressure and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) with NaCl, are compared with those obtained with distilled water. A decrease of the DPPG mean molecular area is observed due to the local diminution of the Na⁺ concentration close to the polar head group and the simultaneous onset of interactions between the amino group of natural polyamines and the polar head group of DPPG. The same effects occur with azhepsi, followed by an insertion of the hydrophobic dimethylsilyl group. Near the polar head groups DPPG, a substitution of the Na⁺ by the amino groups of polyamines occurs.

For the competition experiments, whereas a partial substitution is possible after putrescine and spermine adsorption, it is almost complete after spermine adsorption. Since the number of amino groups of azhepsi and spermine are the same, hydrophobic interactions due to the presence of dimethylsilyl group occur between azhepsi and the alkyl chains of DPPG. This favoured insertion of azhepsi provides a basis for understanding of the action of dimethylsilyl derivatives in the case of an antitumour strategy.     

Adhesion and friction force coupling of gecko setal arrays: implications for structured adhesive surfaces

The extraordinary climbing ability of geckos is partially attributed to the fine structure of their toe pads, which contain arrays consisting of thousands of micrometer-sized stalks (setae) that are in turn terminated by millions of fingerlike pads (spatulae) having nanoscale dimensions. Using a surface forces apparatus (SFA), we have investigated the dynamic sliding characteristics of setal arrays subjected to various loading, unloading, and shearing conditions at different angles. Setal arrays were glued onto silica substrates and, once installed into the SFA, brought toward a polymeric substrate surface and then sheared. Lateral shearing of the arrays was initiated along both the "gripping" and "releasing" directions of the setae on the foot pads. We find that the anisotropic microstructure of the setal arrays gives rise to quite different adhesive and tribological properties when sliding along these two directions, depending also on the angle that the setae subtend with respect to the surface. Thus, dragging the setal arrays along the gripping direction leads to strong adhesion and friction forces (as required during contact and attachment), whereas when shearing along the releasing direction, both forces fall to almost zero (as desired during rapid detachment). The results and analysis provide new insights into the biomechanics of adhesion and friction forces in animals, the coupling between these two forces, and the specialized structures that allow them to optimize these forces along different directions during movement. Our results also have practical implications and criteria for designing reversible and responsive adhesives and articulated robotic mechanisms.     

Vesicle and stable monolayer formation from simple "click" chemistry adducts in water

Click chemistry has been successfully extended into the field of molecular design of novel amphiphatic adducts. After their syntheses and characterizations, we have studied their aggregation properties in aqueous medium. Each of these adducts forms stable suspensions in water. These suspensions have been characterized by dynamic light scattering (DLS) studies and transmission electron microscopy (TEM). The presence of inner aqueous compartments in such aggregates has been demonstrated using dye (methylene blue) entrapment studies. These aggregates have been further characterized using X-ray diffraction (XRD), which indicates the existence of bilayer structures in them. Therefore, the resulting aggregates could be described as vesicles. The temperature-induced order-to-disorder transitions of the vesicular aggregates and the accompanying changes in their packing and hydration have been examined using high-sensitivity differential scanning calorimetry, fluorescence anisotropy, and generalized polarization measurements using appropriate membrane-soluble probe, 1,6-diphenylhexatriene, and Paldan, respectively. The findings of these studies are consistent with each other in terms of the apparent phase transition temperatures. Langmuir monolayer studies confirmed that these click adducts also form stable monolayers on buffered aqueous subphase at the air-water interface.     

Synthesis of a dibenzylchitin-type polysaccharide by acid-catalyzed polymerization

This paper describes the polymerization of 2-methyl-(3,6-di-O-benzyl- 1,2-dideoxy-α-D -glucopyrano)-[2,1-d]-2-oxazoline ( 1 ) with an acid catalyst. The polymerization proceeds involving stereoregular glycosylation to give polysaccharide 2 . The polymer structure, 2-acetamido-3,6-di-O-benzyl-2-deoxy-(l→4)-β-D -glucopyranan was determined by means of ¹H NMR, ¹³C NMR, and IR spectra as well as elemental analysis. The molecular weight was at most 4900 (degree of polymerization ≈ 13).     

The Langmur-blodgett monolayer dipole potential: a smeared dipole model for a lipid array,and pulsing of the potential by direct subphase infusion of immunochemical and lecti/polysaccharide complexes

An important contribution to the surface potential of lipid bilayers and monolayers comes from the intrinsic dipole moment of the lipid molecules. A theoretical model of the monolayer which involves a smeared dipole sheet approximation is introduced. This model is used to explore the nature and origins of the surface potential. In addition, the potential associated with phosphatidyl choline/cholesterol monolayers compressed on a Langmuir-Blodgett trough was measured with a non-contacting electrostatic voltmeter. A trough infusion configuration was fabricated to perform dynamic subphase experiments with compressed films in place. The potential/time response of monolayers to selective bimolecular systems such as antibody-antigen and concanavalin A-saccharide pairs was examined. These reactions induce spontaneous transients in dipole potential of magnitude 20–80 mV and duration of less than 1 s. The potential transients are attributed to local perturbation of lipid orientation and introduction of protein dipole fields caused by the formation of aggregates at the monolayer/water interface.     

Creation of highly stable selenium nanoparticles capped with hyperbranched polysaccharide in water

Water-dispersible selenium nanoparticles (SeNPs) were created by using natural hyperbranched polysaccharide (HBP) as the stabilizer and capping agent under extremely safe conditions. The structure, morphology, size, and stability of the nanocomposites were investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and static and dynamic light scattering (DLS) measurements. The results revealed that the spherical selenium nanoparticles (mean particle size of about 24 nm) were ligated with HBP to form nanocomposites (Se-HBP) in aqueous solution and were stable for over one month. In our findings, supported by the results of FTIR, TEM, AFM, and DLS, SeNPs were capped with the HBP macromolecules, as a result of strong physical adsorption of OH groups on Se surfaces, leading to a highly stable structure of Se nanoparticles in water. This work provided reaction sites for the complexation between HBP and Se to fabricate well-dispersed Se nanoparticles in aqueous system with potential bioapplications.     

Formation and characterization of natural polysaccharide hollow nanocapsules via template layer-by-layer self-assembly

Two different natural zeolites having different phase compositions were obtained from different regions of Turkey and modified by ion-exchange (0.5M NH(4)NO(3)) and acid leaching using 1M HCl. The natural and modified samples were treated at low temperature (LT), high temperature (HT) and steam (ST) conditions and characterised by XRF, XRD, BET, FTIR, DR-UV-Vis, NH(3)-TPD and TGA. Ion-exchange with NH(4)(+) of natural zeolites results in the exchange of the Na(+) and Ca(2+) cations and the partial exchange of the Fe(3+) and Mg(2+) cations. However, steam and acidic treatments cause significant dealumination and decationisation, as well as loss of crystalline, sintering of phases and the formation of amorphous material. The presence of mordenite and quartz phases in the natural zeolites increases the stability towards acid treatment, whereas the structure of clinoptilolite-rich zeolites is mostly maintained after high temperature and steam treatments. The natural and modified zeolites treated at high temperature and in steam were found to be less stable compared with synthetic zeolites, resulting in a loss of crystallinity, a decrease in the surface area and pore volume, a decrease in the surface acidity as well as dealumination, and decationisation.