Surface modification of a biomedical polyethylene terephthalate (PET) by air plasma

In this work, low-pressure air plasma has been used to improve polyethylene terephthalate (PET) surface properties for technical applications. Surface free energy values have been estimated using contact angle value for different exposure times and different test liquids. Surface composition and morphology of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Surface topography changes related with the etching mechanism have been followed by weight loss study. The results show a considerable improvement in surface wettability and the surface free energy values even for short exposure times in the different discharge areas (discharge area, afterglow area and remote area), as observed by a remarkable decrease in contact angle values. Change of chemical composition made the polymer surfaces to be highly hydrophilic, which mainly depends on the increase in oxygen-containing groups. In addition to, the surface activation and AFM analyses show obvious changes in surface topography as a consequence of the plasma-etching mechanism.     

Local surface cleaning and cluster assembly using contact mode atomic force microscopy

Conventional contact mode atomic force microscopy (AFM) has been used for local surface cleaning and cluster alignment. By using the AFM tip to sweep and push in contact mode, we have demonstrated that Cu clusters, prepared by vacuum evaporation onto Dow Cyclotene 3022 polymer and subsequent exposure to atmosphere, can easily be moved by the AFM tip, and assembled at the outer edge of the scanned region to form a line of clusters. We have found that the force applied by the tip plays an important role in the ease of cluster motion. Cyclotene surface treatment that enhances cluster adhesion hinders this ability, and may be used as a method of nanofabrication.     

Surface adhesion between hexagonal boron nitride nanotubes and silicon based on lateral force microscopy

This study presents the surface adhesion between hexagonal boron nitride nanotube (BNNT) and silicon based on lateral manipulation in an atomic force microscope (AFM). The BNNT was mechanically manipulated by the lateral force of an AFM pyramidal silicon probe using the scan mechanism in the imaging mode. With a controlled normal force of the AFM probe and the lateral motion, the lateral force applied to the BNNT could overcome the surface adhesion between BNNT and silicon surface. The individual BNNT is forced to slide and rotate on the silicon surface. Based on the recorded force curve, the calculated shear stress due to surface adhesion is 0.5 GPa. And the specific sliding energy loss is 0.2 J/m². Comparing BNNTs and carbon nanotube (CNT), the shear stress and specific sliding energy loss of BNNT are an order of magnitude larger than that of CNT. Therefore, the results show that the surface adhesion between BNNT and silicon surface is higher than that of CNT.     

An AFM study of the effect of chemical treatments on the surface microstructure and adhesion properties of flax fibres

The mechanical properties of fibre-reinforced polymer composites are largely dependant on the adhesion between the matrix and the fibre. In order to enhance the interaction between flax fibres and unsaturated polyester resins, raw fibres were chemically modified using sodium hydroxide, sodium hydroxide plus acetic anhydride and formic acid-based treatments. The physical properties of the modified fibres were investigated by means of the atomic force microscopy. At first, the morphological analysis of the surfaces shows that after the chemical treatments, the fibres surface appear to be less heterogeneous in topology and smoother. Nonetheless, no significant roughness difference was found between the different treatments. Secondly, adhesion forces measurements were performed between a standard AFM silicon nitride tip and the fibres. The adhesion forces were found to vary according to the chemical treatment. The sodium hydroxide-based treatment was found to increase the adhesion force between the fibre and the AFM tip whereas the lowest adhesion force was found for the formic acid- based treated fibre. These results were attributed to the different hydrophilic character of the modified fibres. Due to the importance of the water layer adsorbed on the fibres, the adhesion forces between the AFM tip and the different samples are found to be mainly dominated by capillary forces in relation with the fibre's surface hydrophilicity.     

Study on the surface properties of wood/polyethylene composites treated under plasma

Wood/polyethylene (PE) composites are widely used in many fields for its excellent properties, but they are hard to adhere for the surface lacking of polarity. So low-pressure glow discharge of air plasma was used to improve the adhesion properties of wood/PE composites. The composites were treated by plasma under different discharge power. And the changes on the surface properties of the treated and untreated composites were studied by contact angle, Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS) analysis. The measurement showed that the contact angle decreased after plasma treatment, and the contact angle decreased gradually with the increasing of discharge power. The FTIR analysis results showed that the polar groups such as hydroxyl, carbonyl and carboxyl were formed on the surface of the composites treated under plasma. SEM and AFM results showed that the roughness of plasma treated samples increased. XPS analysis results indicated that the content of carbon element decreased while the content of oxygen element in the composition of wood/PE composites surface element increased and it reached a balance in a higher power, meanwhile a lot of carboxyl groups were formed. The newly formed polar groups are benefit for the adhesion of composites. The shear bonding strength test showed that the adhesion properties of wood/PE composites improved effectively after plasma treatment.     

Material anisotropy revealed by phase contrast in intermittent contact atomic force microscopy

Phase contrast in intermittent-contact atomic force microscopy (AFM) reveals in-plane structural and mechanical properties of polymer monolayers. This is surprising, because measurements of nanoscale in-plane properties typically require contact mode microscopies. Our measurements are possible because the tip oscillates not just perpendicular but also parallel to the sample surface along the long axis of the cantilever. This lateral tip displacement is virtually universal in AFM, implying that any oscillating-tip AFM technique is sensitive to in-plane material properties.     

Determination of silicone coating Young's modulus using atomic force microscopy

The polymerisation degree of thin polymer coatings was checked by following the variation of their local mechanical properties. Atomic force microscope (AFM) was used in an indentation mode to investigate the mechanical characteristics of silicone coatings on polycarbonate substrates. The evolution of Young's modulus of the silicone coatings was determined as a function of the polymer annealing time. We have used a relative method to measure Young's moduli, which involves a calibration step with a set of reference polymers. No variation was observed for the modulus of silicone coatings annealed during more than 40 min at 130 °C. This result indicates that over-heating does not modify the mechanical properties of the coating.     

Nanotack test: adhesive behavior of single latex particles

We present an investigation of the adhesive properties of latex films with nanometric thickness through force spectroscopy using an atomic force microscope (AFM). The AFM tip can be used to indent and excite mechanically one single latex particle, and provides an adhesion test which resembles macroscopic probe tack test, but at nanometric scales. We show that this AFM nanotack test can be analyzed quantitatively, normalizing the total rupture energy by the contact area formed during the indentation step. This contact area depends upon the mechanical properties and environment of the latex particle.     

Shear modulation force microscopy study of near surface glass transition temperatures

We report results of glass transition (T(g)) measurements for polymer thin films using atomic force microscopy (AFM). The AFM mode, shear modulation force microscopy (SMFM), involves measuring the temperature-dependent shear force on a tip modulated parallel to the sample surface. Using this method we have measured the surface T(g) of thin (17-500 nm) polymer films and found that T(g) is independent of film thickness (t>17 nm), strength of substrate interactions, or even presence of substrate.     

Surface properties of polypropylene/organoclay nanocomposites

Influence of nanoclay amount on surface properties of the nanocomposites was investigated using Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), contact angle measurement, scanning electron microscopy (SEM) and transmission spectroscopy (TS). Polypropylene based nanocomposites containing various loads of nanoclay were prepared by melt compounding. X-ray diffraction (XRD) characterized the dispersion of nanoclay in polymer matrix. AFM and SEM studies have shown increase in surface roughness by raising the amount of nanoclay. Contact angle measurements of the resultant nanocomposites have also shown improvement in wettability related to disperse part of surface tension. POM images illustrated an increase in the number of spherulite simultaneously with a decrease in their size; this result was also supported by differential scanning calorimetry (DSC).     

Structure and frictional properties of Langmuir-Blodgett films of Cu nanoparticles modified by dialkyldithiophosphate

Langmuir-Blodgett (LB) films of dialkyldithiophosphate (DDP) modified Cu nanoparticles were prepared. The structure, microfrictional behaviors and adhesion of the LB films were investigated by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and atomic/friction force microscopy (AFM/FFM). Our results showed that the modified Cu nanoparticles have a typical core-shell structure and fine film-forming ability. The images of AFM/FFM showed that LB films of modified Cu nanoparticles were composed of many nanoparticles arranged closely and orderly and the nanoparticles had favorable behaviors of lower friction. The friction loop of the films indicated that the friction force was affected prominently by the surface slope of the Cu nanoparticles and the microfrictional behaviors showed obvious “ratchet effect”. The adhesion experiment showed that the modified Cu nanoparticle had a very small adhesive force.     

Microstructure and electrical characterization based on AFM of very high-doped polysilicon grains

In this work, we demonstrate that atomic force microscopy allows topography measurement as well as the local electrical properties of very high-doped polysilicon film prior to any subsequent annealing. AFM and TEM observations showed the columnar microstructure of the polysilicon layer. The electrical effect of this microstructure was characterized using SCM, KFM and C-AFM. Each electric mode gives additional information on the local properties of the polysilicon layer.     

Surface adhesion properties of graphene and graphene oxide studied by colloid-probe atomic force microscopy

Surface adhesion properties are important to various applications of graphene-based materials. Atomic force microscopy is powerful to study the adhesion properties of samples by measuring the forces on the colloidal sphere tip as it approaches and retracts from the surface. In this paper we have measured the adhesion force between the colloid probe and the surface of graphene (graphene oxide) nanosheet. The results revealed that the adhesion force on graphene and graphene oxide surface were 66.3 and 170.6 nN, respectively. It was found the adhesion force was mainly determined by the water meniscus, which was related to the surface contact angle of samples.     

Correlation of atomic force microscopy detecting local conductivity and micro‐Raman spectroscopy on polymer–fullerene composite films

Thin hetero‐junction composite films of polymer (electron donor) and fullerene (electron acceptor) are prepared on indium‐tin‐oxide coated glass by spin‐coating from solution in dichlorobenzene. Optimized atomic force microscopy (AFM) parameters allowed us to scan these soft composite films in contact mode and to measure their local conductivity with high lateral resolution by current‐sensing AFM. The morphology and local conductivity data are correlated with Kelvin force microscopy and micro‐Raman mapping and discussed with view to their photovoltaic properties. Regions with both compounds present are compared to areas where the components segregated, acting as shunts of the junction. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of biopolymer networks by means of AFM

Natural hydrogel alginate was investigated by means of atomic force microscopy (AFM) to gain microscale information on the morphological and rheological properties of the biopolymer network cross-linked by various cations. Local rheological properties of the gels measured by force spectroscopy gave correlation between increasing ion selectivity and increasing polymer elasticity. Adhesive forces acting between the surface of the gel and the probe, and also the intrinsic rheological properties of bulk polymers affect the microscopical image formation.     

Gradients of topographical structure in thin polymer films

We report the fabrication of centimeter-long gradients of topography. Structured polymer thin films were made by spin-coating an immiscible poly(methyl methacrylate)/poly(2-vinylpyridine) (PMMA/P2VP) blend from a common solvent on a substrate presenting a surface-energy gradient. Due to the interplay between polymer-wetting of the substrate and polymer phase-separation, different morphologies were observed along the sample. Atomic force microscopy (AFM) revealed a gradual transition from a flat to a structured morphology as the surface energy of the substrate was reduced. The transition occurred for a well-defined range of surface energies. A selective solvent was used to remove one of the polymer phases, increasing the topographical contrast and providing insight into the different stages of the transition. Image analysis allowed a quantitative characterization of the structure gradient.     

Photo-irradiation effects on the surface morphology of poly(p-phenylene vinylene) films

In this work, we have studied the surface morphology of photo-irradiated poly(p-phenylene vinylene) (PPV) thin films by using atomic force microscopy (AFM). We have analyzed the first-order statistical parameters, the height distribution and the distance between selected peaks. The second-order statistical analysis was introduced calculating the auto-covariance function to determine the correlation length between heights. We have observed that the photo-irradiation process produces a surface topology more homogeneous and isotropic such as a normal surface. In addition, the polymer surface irradiation can be used as a new methodology to obtain materials optically modified.     

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.     

Surface investigation of adhesive formulation consisting of UV sensitive triblock poly(styrene–b-butadiene–b-styrene) copolymer

Atomic force microscopy (AFM) analysis in conjunction with macroscopic studies such as peel testing and contact angle measurement have been undertaken to explain the nanomechanical properties of adhesive formulation consisting of triblock poly(styrene–b-butadiene–b-styrene) (SBS) copolymers. The cross-linking of this photosensitive copolymer was investigated by analyzing the mechanical and morphological changes of each phase induced by the UV exposure. Main result is that the adhesive properties are strongly influenced by the cross-linking of the polybutadiene (PB) phase leading to an increase in the surface stiffness without affecting the surface energy. AFM analysis shows that the adhesion force is mostly governed by the contact area between the adhesive and the probe. The surface mobility may explain the increase in adhesion for this pressure sensitive copolymer.     

Study on the nano machining process with a vibrating AFM tip on the polymer surface

The polymer has been proved to be nano machined by a vibrating tip in tapping mode of Atomic Force Microscope (AFM). The force between the tip and the surface is an important factor which determines success of the machining process. Controlling this force with high accuracy is the foundation of nanomachining in AFM tapping mode. To achieve a deeper understanding on this process, the tip is modeled as a driving oscillator with damping. Factors affecting the nano machining process are studied. The Hertz elastic contact theory is used to calculate the maximum contact pressure applied by the tip which is employed as a criterion to judge the deformation state of the sample. The simulation results show that: The driven amplitude can be used as a main parameter of controlling the machined depth. Sharper tips and harder cantilevers should be used for successful nanomachining with the vibrating tip. Under the same conditions, a larger tip radius will not only result in the machining error, but also lead to failure of the nanomachining process. The higher driving frequency will lead to a larger tapping force. However it cannot be used as a parameter to control the machined depth because of its narrow variation range. But it is a main error source for the nanomachining process in AFM tapping mode. Moreover, a larger Young's modulus polymer sample will induce a smaller machined depth, a larger maximum contact pressure and a bigger tapping force.