Micromechanical properties of glassy and rubbery polymer brush layers as probed by atomic force microscopy

Carboxylic acid terminated polystyrene and polybutylacrylate were grafted from melt onto a silicon substrate modified with the epoxysilane monolayer. The tethered layers fabricated from polymers of different molecular weights are smooth, uniform, mechanically stable, and cover homogeneously the modified silicon surface. Micromechanical properties of the dry glassy and rubbery brush layers were measured with atomic force microscope. We observed that for the PS layers with the thickness higher than 7 nm, the average value of the elastic moduli reached 1.1 GPa, which is close, but still lower than the expected for bulk polymer. The elastic modulus of PS polymer brush layers dramatically depends upon molecular weight and follows the inverse law with segment molecular weight, M_c of 18,000 known for bulk PS. This result indicates that the process of the formation of the physical network within polymer melt of chains tethered to a solid substrate is similar to that occurring in unconstrained polymer melt. Under these conditions, three PS brush layers studied in this work represent different cases of chains without stable entanglements for M<M_c as well as chains with stable entanglements for brushes with M∼M_c. This transition shows itself in significant reduction of the compliance reflected in twofold increase in elastic modulus. Our estimation predicts that modest lowering of ‘limiting’ elastic modulus of 1.4 GPa can be expected for thicker polymer brushes.     

Introducing open films of nanosized cellulose—atomic force microscopy and quantification of morphology

A method for preparing open, sub-monolayer cellulose films on a silicon substrate is introduced, and the open films were quantified using the three-dimensional information from atomic force microscopy (AFM) height images. The preparation method is based on spin coating low concentrations of trimethylsilyl cellulose (TMSC) on silicon and hydrolysing the TMSC to cellulose using a vapour phase acid hydrolysis. AFM showed that the surfaces consist of nanosized cellulose patches which are roughly 50-100 nm long, 20 nm wide, and 1 nm high. The volume of the cellulose patches was quantified. Examination of the cross section of the cellulose patches revealed that the exaggeration of the lateral dimensions by the AFM tip is small enough to account for a mere ±2% error in the volume quantification. Pilot experiments showed that the volume of the cellulose was largely restored in a wetting/drying cycle but the morphology changed considerably. Because of their small size, the cellulose patches provide a novel approach for interpretation on the molecular architecture of cellulose.     

New applications in studies of waterborne coatings by atomic force microscopy

Atomic force microscopy (AFM) is rapidly emerging as an important tool for coatings characterization. We report several new applications of AFM of particular value to the development of improved waterborne coatings systems. First, an AFM method was developed to quantitatively assess the extent of coalescence and film formation for latex films by measurement of particle number density of protruding (uncoalesced) particles in dried coatings. Second, the use of topographic imaging to evaluate environmental (temperature) effects on film formation was investigated for a waterborne latex system. Finally, specular gloss of waterborne epoxy coatings was studied by AFM and optical measurements, and topographic features analyzed using power spectral density calculations were found to correlate with optical gloss measurements. Mechanisms for gloss reduction over time (particularly in early pot life coatings) were elucidated in the studies. Further applications in coatings studies will be driven by the development of new modes of AFM (friction force, force modulation, and phase contrast) that can be used to map mechanical properties (friction, stiffness, and adhesion) while simultaneously imaging topography. Examples of the use of the phase contrast mode to identify chemically different domains in early pot life waterborne epoxy coatings are presented.     

Growth process of homogeneously and heterogeneously nucleated spherulites as observed by atomic force microscopy

A poly(bisphenol A octane ether) (BA-C8) was synthesized. The isothermal spherulitic growth process was studied in situ using atomic force microscopy (AFM) at room temperature. For spherulites formed by homogeneous nucleation, the growth process includes the birth of a primary nucleus, the development of a founding lamella and the growth of the founding lamella into a spherulite. An embryo below a critical size is unstable. A stable embryo grows into a founding lamella. There is only one founding lamella in each spherulite. All other lamellae originate from this founding lamella. Two eyes can be seen at the center of a spherulite. For spherulites formed through heterogeneous nucleation, many lamellae grow at the nucleus surface and propagate outward radially. The spherulites acquire spherical symmetry at the early stage of crystallization. No eyes are found for this kind of spherulites.     

Single polymer chain rubber elasticity investigated by atomic force microscopy

A method, which is called as ‘nanofishing’, enabled us to stretch a single polymer chain adsorbed on an Au(111) substrate with picking it at its two thiol-modified termini using atomic force microscope equipped with a gold-coated probe. A force-extension curve obtained for a single polystyrene chain in a Θ solvent (cyclohexane) showed a good agreement with a so-called worm-like chain model, and thus gave microscopic information about entropic elasticity. Solvent effects on the statistical properties of single polymer chains were also investigated. For example, the second virial coefficient in cyclohexane was determined at a single polymer basis, which was almost comparable with a simple Flory's lattice model.     

Surface crystallization of poly(ethylene terephtalate) studied by atomic force microscopy

Poly(ethylene terephtalate) (PET) crystallization was shown by atomic force microscopy (AFM) to occur at 85 °C in the first few nanometers near the polymer-air interface. The surface was fully transformed into spherulites after 30 min, while no signs of bulk crystallization were observed by FTIR. All the observed spherulites presented a nucleation centre, indicating that the crystallization process started at the surface of the film. Tapping mode AFM confirmed that the spherulites were not covered by an amorphous layer. The most probable explanation is a decrease of T_g near the surface. Due to the poor crystallization conditions, the constitutive units of the spherulites were small crystalline blocks. By changing the annealing time, it was possible to produce PET surfaces with different surface fractions consisting of semi-crystalline material (spherulites) and amorphous matrix. This provided a controlled surface heterogeneity on the submicrometer scale, with a contrast in terms of stiffness, roughness and swelling by organic solvents.     

Crystal growth of faujasite observed by atomic force microscopy

Atomic force microscopy (AFM) was employed to reveal the crystal growth mechanism of faujasite. The seeded growth of faujasite in dilute aluminosilicate solutions was observed. Two solutions were prepared: one was near equilibrium with the seed and the other was in growth mode for the seed. Morphological changes during the seeded growth were observed along with the growth period at the same position on the seed (ex situ observation). These observations showed the rough surface of the seed changing into a well-ordered (1 1 1) face in the solution that was near equilibrium with the seed. This surface ordering proceeded by thermodynamic stabilization of the top-surface structure via the mutual transfer of aluminosilicate species between the solution and solid phases, and/or by the dissolution of the amorphous matter on the seed. In growth mode, most of the top surfaces of the seeded crystals were terminated by double six-membered rings (D6Rs), while some were by complete or incomplete sodalite cage. These results showed that aluminosilicate species equal to or smaller than 6R contributed to the crystal growth.     

Lamellar morphology of random metallocene propylene copolymers studied by atomic force microscopy

Four sets of propylene based random copolymers with co-units of ethylene, 1-butene, 1-hexene and 1-octene, and a total defect content up to ∼9 mol% (including co-unit and other defects), were studied after rapid and isothermal crystallization. Etched film surfaces and ultramicrotomed plaques were imaged so as to enhance contrast and minimize catalyst and co-catalyst residues. While increasing concentration of structural irregularities breaks down spherulitic habits, the formation of the gamma polymorph has a profound effect on the lamellar morphology. Lamellae grown in the radial axis of the spherulite and branches hereon are replaced in γ-rich copolymers with a dense array of short lamellae transverse or tilted to the main structural growth axis. This is the expected orientation for γ iPP branching from α seeds. Spherulites are formed in copolymers with non-crystallizable units (1-hexene and 1-octene) up to ∼3 mol% total defect content and were observed up to ∼6 mol% in those with partially crystallizable comonomers (ethylene and 1-butene). However, lamellae were observed in all the copolymers analyzed, even in the most defective ones, highlighting the important role of the gamma polymorph in propagating lamellar crystallites in poly(propylenes) with a high concentration of defects. Long periods measured from AFM and SAXS are comparatively analyzed.     

Physical evaluation of pure zein films by atomic force microscopy and thermal mechanical analysis

Biodegradable edible films can be made from corn protein, α-zein. Pure zein films are cast from an organic solution of α-zein. This report outlines the surface conditions of such pure zein films. First, the transition temperature, T _t′ of the pure zein film was measured with a thermomechanical analyzer. T _t was between 167.0 and 172.7°C. The thermal elongation of the films depended on the drying conditions used during film preparation. Second, the surface microstructure of pure zein films, produced under several different drying conditions, was observed by atomic force microscopy. The surface had a morphology that showed depressions either with acutely (90–120°) or obtusely (121–180°) angled features depending upon the drying conditions. On the other hand, the surface microstructure after thermal elongation analysis appeared to have a pattern of projections that was repeated every 25 nm. Third, we measured the contact angle of the pure zein films. We found a correlation between surface microstructure and contact angle. Pure zein films with projections smaller than 200 nm in base diameter on the surface had a high contact angle (>70°).     

In situ atomic force microscopy of the melting of melt-crystallized polyethylene

High temperature AFM is used to observe the melting of polyethylene lamellae crystallized from the melt in situ in real-time. Both oriented and un-oriented samples are observed. The melting of shish-kebab structures, including revealing the bare oriented shish, is achieved. Lamellae are observed to melt from their edges, and this is proposed to be due to the inherent higher mobility at the crystal edges rather than differences in stability within the crystal due to different levels of post crystallization perfecting. Observation of the melting of structures that have been observed during growth confirms that material crystallized at lower temperatures melts first, followed by material crystallized in confined geometries, and finally the rest of the isothermally crystallized lamellae that melt back from the edges with an apparently random morphology that is not the reverse of the growth process. In situ observation during melting is confirmed as an alternative and complementary technique to etching to reveal behaviour during crystallization when crystallization is too rapid for in situ observation.     

Micromorphological characterization of polymer-oxide nanocomposite thin films by atomic force microscopy and fractal geometry analysis

The purpose of this study was to evaluate the 3-D surface micromorphology of polymer-oxide thin films spin-coated from a composite of poly-methyl-methacrylate as the matrix and elongated titania nanorods as the filler particles. The surfaces of these composite films were investigated by atomic force microscopy and characterized by fractal geometry analysis. The effect of increasing loading of the fillers between 0 and 30% by weigth relative to the matrix was assessed. An increasing roughness was observed, with typical emergence of protruding ripples progressively extending into larger stripes. The amplitude parameters of the surfaces were determined by analysis of the height distributions. The fractal analysis of roughness revealed that the films have fractal geometry. Triangulation method based on the linear interpolation type was applied to determine the fractal dimension. A connection was observed between the surface morphology and the physical properties of the coatings as assessed in previous works.     

Observations and morphological analysis of supermolecular structure of natural bitumens by atomic force microscopy

The supermolecular structures of natural bitumens of the thermal consequent row asphaltites ⇒ lower kerites (albertites) ⇒ higher kerites (impsonites) ⇒ anthraxolites from the Timan-Pechora petroleum province and Karelian shungite rocks, Russia, were studied in details.The experimental technique used was atomic force microscopy (AFM), following fracture preparation. The element distribution of the sample surfaces was analyzed by an X-ray microanalyser “Link ISIS”, combined with a scanning electron microscope (SEM).In this work, we characterized the supermolecular evolution of natural solid bitumens in the carbonization sequence by quantitative parameters. We showed that supermolecular structure can be important in defining to which classification group solid bitumens belong.     

Study on the adsorption of poly(o-ethoxyaniline) nanostructured films using atomic force microscopy

Nanostructured films of poly(o-ethoxyaniline) (POEA) were studied by atomic force microscopy (AFM), which indicated a globular morphology for films containing one or more layers of POEA. Consistent with the nucleation and growth model for the adsorption process, the mean roughness and fractal dimension were found to increase with the time of adsorption and with the number of POEA layers in the initial stages of adsorption, reached maximum values and then decreased after 10 min of adsorption or after deposition of five POEA layers. Such behavior has been explained in terms of the decrease in the film irregularities, with voids being filled with polymeric material leading to smoother surfaces.     

Latex film formation: atomic force microscopy and theoretical results

We have critically examined the kinetics of latex film formation using an atomic force microscope to obtain corrugation height data as a function of time, temperature, molecular weight, particle size, etc. The results show that the film forming process obeys viscoelastic time/ temperature superposition principles, thus indicating a direct relationship between the kinetics of film formation and rheological properties. Film formation kinetics are examined under ‘wet’ and ‘dry’ conditions, with film formation occurring almost ten-times faster under wet conditions than dry. This proves for the latex system examined that capillary pressure from the water meniscus is the dominant driving stress for film formation. Past theories for latex film formation are reviewed, and problems and deficiencies are noted. A new theory for film formation from a dry latex system is presented, which is based on the use of the Boltzmann Superposition Principle to relate the changing stress and strain fields as the latex particles deform. The predictions of theory and the experimental data show excellent agreement over nearly four decades of time.     

Surface structure of Kevlar® fiber studied by atomic force microscopy and inverse gas chromatography

Kevlar® fiber surface structure was primarily and directly observed in the filament configuration by the tapping mode atomic force microscopy (AFM). The microfibrils feature was observed with an average width of 500 nm, composed of various types of periodical units of an average size 50 nm in a pleating appearance. At the less crystalline spot on the Kevlar® fiber surface, the periodical organizations exhibit the skin-core-like differentiation. In contrast, at the highly crystalline spot, the periodicity is more uniformly arranged by a rectangular network manner. Inverse gas chromatography (IGC) was used as a tool to investigate the surface structure heterogeneity by calculating the surface energy of different types of probes adsorbed on the Kevlar® fiber surface. The energy sites distribution plot of n-hexylamine adsorption at finite dilution exhibits a two-adsorbing-peaks curve. At the higher energy site, a possible hydrogen-bonding interaction was proposed between n-hexylamine and oxygen-containing groups formed at the less crystalline surface. According to the AFM and IGC results, a Kevlar® fiber surface organizations model at the nanometer scale was proposed.     

Characterization of biaxially oriented polypropylene films by atomic force microscopy and microthermal analysis

A new method for evaluating the thermal properties of the films and detecting fabrication failures has been provided. Moreover, this article studies the characterization of biaxially oriented polypropylene films (BOPP) using the Microthermal Analizer (μTA 2990). This instrument combines high‐resolution imaging capabilities of the atomic force microscopy (AFM) with physical characterization by thermal analysis. In the first part of the work, topographic images of the film surfaces were obtained by AFM. They showed that the fabrication process and additives to the films caused differences in the sample topography. In the second part, the thermal conductivity images of multilayer films were obtained by thermal analysis mode. The thickness of each layer was determined for several BOPP films, based on the thermal conductivity signal registered by μTA 2990. Finally, it has been proven that this new technique is valid for detection of thermal transitions in polymer samples. Thus, melting points and glass transitions were measured in the samples with thermal probe. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1553–1561, 2002.     

Temperature dependent loss tangent measurement of polymers with contact resonance atomic force microscopy

The loss tangent of individual components in a blend of polypropylene (PP) and polystyrene (PS) is measured as a function of temperature with contact resonance atomic force microscopy. The loss tangent is calculated directly from the experimentally obtained contact resonance frequency, cantilever quality factor and other operating parameters. The temperature dependent variation of the loss tangent, measured at the high frequency of AFM measurements, shows peaks at different temperatures for the different polymer materials. The loss tangent peak at approximately 53 °C for PP is identified as an alpha peak signifying crystal relaxation while the loss tangent peak at approximately 75 °C for PS is identified as a glass transition.     

Measuring local viscoelastic properties of complex materials with tapping mode atomic force microscopy

Tapping mode atomic force microscopy is a technique to measure the topography and properties of surfaces involving a micro-cantilever with a tip at one end that is excited into an oscillation near its resonance frequency. The phase lag between the excitation signal and the observed oscillation is sensitive to local mechanical properties under certain experimental conditions. We have found that by using silicon as an internal standard reference surface we can unambiguously relate the phase lag to local viscoelastic properties of a polymeric material. A model describing this relation has been built, validated with experimental data and finally inverted such that it can be used to determine local properties. This allows us to measure high frequency local viscoelastic properties on length scales as small as several nanometers. This technique works well for relatively compliant polymer surfaces with a shear modulus less than about 1 GPa.     

Surface phase separations of PMMA/SAN blends investigated by atomic force microscopy

The thin films of poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN) and their blends were prepared by means of spin-coating their corresponding solutions onto silicon wafers, followed by being annealed at different temperatures. The surface phase separations of PMMA/SAN blends were characterized by virtue of atomic force microscopy (AFM). By comparing the tapping mode AFM (TM-AFM) phase images of the pure components and their blends, surface phase separation mechanisms of the blends could be identified as the nucleation and growth mechanism or the spinodal decomposition mechanism. Therefore, the phase diagram of the PMMA/SAN system could be obtained by means of TM-AFM. Contact mode AFM was also used to study the surface morphologies of all the samples and the phase separations of the blends occurred by the spinodal decomposition mechanism could be ascertained. Moreover, X-ray photoelectron spectroscopy was used to characterize the chemical compositions on the surfaces of the samples and the miscibility principle of the PMMA/SAN system was discussed.     

Determination of the influence of the polymer structure and particle size on the film formation process of polymers by atomic force microscopy

The particle size and morphology of a synthetic polymer latex were shown to influence the film formation behavior. Theoretical models predict that small particles coalesce more easily than large colloids do.The influence of particle size and morphology of differently structured lattices on the film-formation process was investigated by atomic force microscopy (AFM). Sequences of AFM images were acquired over a certain temperature range or at room temperature as a function of time. From the resulting images the average particle diameter of the latex particles in the surface layer was determined as a function of the time or temperature. The resulting curves could be compared to observe differences in the film formation kinetics of the different lattices. These AFM studies confirmed that the film formation behavior is influenced by the particle size and particle morphology, but that the core/shell ratio of core-shell particles has no significant influence on the film formation kinetics.