Morphological analysis of linear low density polyethylene films by atomic force microscopy

Atomic force microscopy has been used to investigate the morphology of hexene linear low density polyethylene (LLDPE) blown film in the undrawn and drawn states. The morphology of the undrawn film, which is biaxially oriented due to the nature of the extrusion process, is composed of crystallites, which consist of aggregates of lamellae. Elongation of the film caused these crystallites to undergo deformation, resulting in the gradual formation of a fibrillar structure in the draw direction. The transformation of these crystallites into fibrils corresponded with an initial increase in the surface roughness, until 250% elongation. Further extension of the film to 450% caused the surface roughness to reach a plateau. The changes observed in the surface roughness and morphology indicate that drawing of the film caused the crystallites to tilt and slip, rupturing crystalline blocks, which then develop into a fibrillar structure. Further extension of these initial fibrillar structures resulted in a more oriented fibrillar morphology. Wide‐angle x‐ray scattering clearly showed the orientation of the crystals with respect to the draw direction throughout the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 777–784, 2002     

Microscopic lamellar organization in high-density polyethylene banded spherulites studied by scanning probe microscopy

Surface topography and lamellar aggregation structure of high-density polyethylene (HDPE) banded spherulites were investigated by scanning probe microscopy. HDPE films were prepared by isothermal crystallization at various crystallization temperatures from the melt. Polarizing near-field scanning optical microscopic (NSOM) observations for the HDPE films revealed submicron-scale correlation between surface topography and birefringence of banded spherulites. The height profile of the film surface along the spherulitic radius periodically changed corresponding to the intensity profile of transmitted light along the radius of the extinction ring. This correlation was more clearly observed in the topographic and NSOM images of permanganic etched PE films. Therefore, it was apparently suggested that the crystallographic c-axis of the orthorhombic unit cell was parallel and perpendicular to the film surface at the peak and the valley in the surface corrugation of the banded spherulite, respectively. The band spacing obtained by polarizing NSOM and atomic force microscopy (AFM) was comparable to that determined by polarizing far-field optical microscopic observation under crossed nicols. The band spacing and the peak-to-valley height difference in the corrugation increased with an increase in isothermal crystallization temperature. AFM observations directly indicated local lamellar orientation and stacking manner.     

Ligand-directed immobilization of proteins through an esterase 2 fusion tag studied by atomic force microscopy

Atomically flat mica surfaces were chemically modified with an alkyl trifluoromethyl ketone, a covalent inhibitor of esterase 2 from Alicyclobacillus acidocaldarius, which served as a tag for ligand-directed immobilization of esterase-linked proteins. Purified NADH oxidase from Thermus thermophilus and human exportin-t from cell lysates were anchored on the modified surfaces. The immobilization effectiveness of the proteins was studied by atomic force microscopy (AFM). It was shown that ligand-esterase interaction allowed specific attachment of exportin-t and resulted in high-resolution images and coverage patterns that were comparable with immobilized purified protein. Moreover, the biological functionality of immobilized human exportin-t in forming a quaternary complex with tRNA and the GTPase Ran-GTP, and the dimension changes before and after complex formation were also determined by AFM.     

A morphological study of melt‐spun polypropylene filaments by atomic force microscopy

Surface morphology of melt‐spun polypropylene (PP) filaments, spun from an additive‐free PP powder and from a commercial‐grade PP with different draw ratios, were examined with atomic force microscopy (AFM). The surface morphology of as‐spun filaments was spherulitic. The gradual transformation of the surface structure from a spherulitic morphology to a fibrillar morphology during stretching was studied. In the filaments spun from the commercial‐grade PP, the transformation was initiated by deformation of spherulites with a draw ratio of 1.2 and continued with association of lamellar stacks into fibrillar chains with a draw ratio between 1.2 and 2.0. A hierarchical morphological microstructure of fibrils, microfibrils, and nanofibrils was developed with a draw ratio of 4.0. In the filaments spun from the additive‐free PP, the association of lamellar stacks into fibrillar morphology occurred considerably later, between draw ratios of 2.0 and 4.0. An oriented lamellar structure was found in these filaments, still with a draw ratio of 4.0. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1242–1249, 1999     

Self‐assembled multilayer films based on diazoresins studied by atomic force microscopy/friction force microscopy

The layer‐by‐layer self‐assembled NDR‐PSS (nitro‐containing diazoresin‐polysodium p‐styrenesulfonate) films were fabricated. The crosslinking structure formed from the conversion of ionic bond to covalent bond after UV irradiation, confirmed by small angle X‐ray diffraction. The roughness and microtribological properties of NDR‐PSS films were investigated by atomic force microscopy/friction force microscopy. The ordered multilayer films after photoreaction are better in microtribological performance than that of the monolayer film. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 631–638, 2000     

Direct observation of the main cell wall components of straw by atomic force microscopy

Cellulose, hemicellulose, and lignin are the main cell wall components of straw. After removal of the wax and the major portion of lignin, the remaining components of the cell wall surface of straw were determined by atomic force microscopy, which revealed a network structure of cellulose and hemicellulose, and some lignin localized on the surface of the network, consistent with the cell wall model suggested by other researchers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2055–2059, 2003     

Increased conductance of individual self-assembled GeSi quantum dots by inter-dot coupling studied by conductive atomic force microscopy

ABSTRACT: The conductive properties of individual self-assembled GeSi quantum dots (QDs) are investigated by conductive atomic force microscopy on single-layer (SL) and bilayer (BL) GeSi QDs with different dot densities at room temperature. By comparing their average currents, it is found that the BL and high-density QDs are more conductive than the SL and low-density QDs with similar sizes, respectively, indicating the existence of both vertical and lateral couplings between GeSi QDs at room temperature. On the other hand, the average current of the BL QDs increases much faster with the bias voltage than that of the SL QDs. Our results suggest that the QDs' conductive properties can be greatly regulated by the coupling effects and bias voltages, which are valuable for potential applications.     

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.     

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.     

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.     

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.     

Surface morphology and nodule formation mechanism of cellulose acetate membranes by atomic force microscopy

By the use of atomic force microscopy (AFM), formation mechanism of nodular structure in cellulose acetate membranes was systematically investigated. Elementary factors affecting the nodule formation were delineated on the basis of both kinetic and thermodynamic considerations. It was shown that (1) the exact nature of nodular structure is thermodynamic equilibrium glassy state; nodular structure will vanish in the rubbery state; (2) the thermodynamic factor affecting nodule formation is the membrane formation temperature; with the membrane formation temperature decreasing, more chain segments are able to form nodular structures; (3) nodule formation is dependent on the segment rearrangement; variation of the solvent environment is the major kinetic factor affecting the segment rearrangement and nodule formation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1328–1335, 2003     

Understanding weathering of oil sands ores by atomic force microscopy

Effect of weathering on colloidal interactions between bitumen and oil sands solids was studied by atomic force microscopy (AFM). The change in bitumen chemistry due to weathering was found to have a negligible effect on the interactions of bitumen with solid particles. However, the increase in solid surface hydrophobicity due to ore weathering reversed the long‐range interaction forces between bitumen and solids from repulsive to attractive with a corresponding increase in adhesion force. The measured force profiles between bitumen and various solids can be well fitted with the extended DLVO theory by considering an additional attractive force. The attractive long‐range force and increased adhesion force make the separation of bitumen from solids more difficult and the attachment of fine solids on liberated bitumen easier, thereby leading to poor bitumen liberation and lower aeration efficiency. Such changes account for the observed poor processability of the weathered ores. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Tribological analysis of glass fibers using atomic force microscopy (AFM)/lateral force microscopy (LFM)

By using atomic force microscopy (AFM)/lateral force microscopy (LFM), a comparative study of the topography as well as the tribological properties (at a micrometer scale) of sized E‐glass fibers was done. Normal and lateral deflection signals are recorded when an AFM tip scans a fiber surface. Friction force data were obtained from the forward and backward scans of lateral force images whose contrasts reveal differences in friction coefficient values and, hence, surface chemical heterogeneity of certain‐sized glass fibers. Sizes having an epoxy film former lead to a higher friction coefficient value than those containing a starch film former. Moreover, the epoxy‐containing size is more readily plowed by the AFM tip. Annealing of this size lowers its friction coefficient. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1013–1025, 2000     

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.     

Phase structural analyses of polyethylene extrusion coatings on high‐density papers. I. Monoclinic crystallinity

In the present work the morphology of high‐density polyethylene (HDPE) extrusion coating layer on high‐density paper (HDP) has been investigated. An uneven layer with a high content of crystallinity against the paper surface was discovered. The methods applied were solid‐state ¹³C NMR Spectroscopy and Atomic Force Microscopy. The highly crystalline layer was found to be mainly monoclinic crystallinity. The formation of the monoclinic crystallites was probably initiated by orientation of the polyethylene molecules by drawing, adhesion to the fibrous paper surface, and pressure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 218–225, 2004     

Morphology of high-density polyethylene pipes stored under hydrostatic pressure at elevated temperature

The morphology of unimodal and bimodal high-density polyethylene (HDPE) pipes during a hydrostatic pressure test was studied in detail using ¹H solid-state NMR. Characterizing the changes of the molecular network during such a test is of key importance for understanding the long-term properties of different HDPE pipe grades. The changes in amount, thickness, and molecular mobility of the crystalline phase, the interface, and the amorphous phase of the two pipe grades with the storage time have been quantified for the first time. The most sensitive microscopic parameter to storage is the molecular mobility of the amorphous phase, with the strongest changes shown by the unimodal HDPE. The density of the tie-molecules is not the main factor controlling the very different behavior of the two pipe grades, but rather it is the density of the entanglements. The NMR results offer unprecedented insights into the changes in the molecular network and support existing deformation models.     

Real-time deflection and friction force imaging by bimorph-based resonance-type high-speed scanning force microscopy in the contact mode

We report herein an alternative high-speed scanning force microscopy method in the contact mode based on a resonance-type piezoelectric bimorph scanner. The experimental setup, the modified optical beam deflection scheme suitable for smaller cantilevers, and a high-speed control program for simultaneous data capture are described in detail. The feature of the method is that the deflection and friction force images of the sample surface can be obtained simultaneously in real time. Images of various samples (e.g., a test grating, a thin gold film, and fluorine-doped tin oxide-coated glass slides) are acquired successfully. The imaging rate is 25 frames per second, and the average scan speed reaches a value of approximately 2.5 cm/s. The method combines the advantages of both observing the dynamic processes of the sample surface and monitoring the frictional properties on the nanometer scale.

PACS

07.79.Lh; 07.79.Sp; 68.37.Ps     

Surface morphology of Nafion 117 membrane by tapping mode atomic force microscope

Surface morphology of Nafion 117 membrane was studied by tapping mode atomic force microscopy. Three different samples were analyzed and correspond respectively to dry membrane and wet membrane equilibrated either with water or with tributylphosphate. These studies show the supermolecular structure of the membrane, which is made of nodules or spherical grains of a mean diameter of 11 nm, and are surrounded by interstitial regions of a mean thickness of 50 Å. Roughness analysis of the samples shows the influence of the swelling properties of the membrane on its surface morphology. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 503–508, 1998