Partial dewetting of polyethylene thin films on rough silicon dioxide surfaces

The effect of roughness on the dewetting behavior of polyethylene thin films on silicon dioxide substrates is presented. Smooth and rough silicon dioxide substrates of 0.3 and 3.2-3.9 nm root-mean-square roughness were prepared by thermal oxidation of silicon wafers and plasma-enhanced chemical vapor deposition on silicon wafers, respectively. Polymer thin films of approximately 80 nm thickness were deposited by spin-coating on these substrates. Subsequent dewetting and crystallization of the polyethylene were observed by hot-stage optical microscopy in reflection mode. During heating, the polymer films melt and dewet on both substrates. Further observations after cooling indicate that, whereas complete dewetting occurs on the smooth substrate surface, partial dewetting occurs for the polymer film on the rough surface. The average thickness of the residual film on the rough surface was determined by ellipsometry to be a few nanometers, and the spatial distribution of the polymer in the cavities of the rough surface could be obtained by X-ray reflectometry. The residual film originates from the impregnation of the porous surface by the polymer fluid, leading to the observed partial dewetting behavior. This new type of partial dewetting should have important practical consequences, as most real surfaces exhibit significant roughness.     

Unique molecular orientation in a smectic liquid crystalline polymer film attained by surface-initiated graft polymerization

Liquid crystalline (LC) polymer brushes containing a mesogenic azobenzene (Az) moiety are synthesized on a quartz or silicon substrate by surface-initiated atom transfer radical polymerization. The molecular orientation of the Az units and the LC properties in the grafted chains are evaluated by UV-vis spectroscopy, polarized optical microscopy, and grazing incidence X-ray diffraction measurements. The Az side chains of the grafted chains exhibited a smectic LC phase in which the smectic layers are oriented perpendicular to the substrate with a parallel orientation of the mesogens. In contrast, a spincast film of the identical LC polymer without grafting to the surface shows layer structures parallel to the substrate. A drastic effect of tethering one end to the substrate on the LC orientation is demonstrated.     

Influence of substrate nature and growth conditions on the morphology of thin DMOAP films

We report some preliminary results on the morphology of thin N,N -dimethyl-n-octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) films. When deposited on a glass substrate, DMOAP forms a mono- or multi-layer structure parallel to the substrate. The surface topography of the film is probed by atomic force microscopy. In general, the free surface of such a film is not flat and smooth. Islands and holes are formed on the free surface of the films when a sufficiently flat substrate is used. The thin film surface topography depends strongly on the nature of the bare substrate, the curing conditions, and the immersion time of the substrate in the DMOAP solution. The film is always rougher than the bare substrate used. Annealing roughens the surface of the alkoxysilane thin films deposited on a glass substrate. For films on glass plates covered with an indium tin oxide layer, annealing has minor effects. The surface topography affects the microstructure of homeotropic smectic samples.     

Influence of substrate nature and growth conditions on the morphology of thin DMOAP films

We report some preliminary results on the morphology of thin N,N -dimethyl- n -octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) films. When deposited on a glass substrate, DMOAP forms a mono- or multi-layer structure parallel to the substrate. The surface topography of the film is probed by atomic force microscopy. In general, the free surface of such a film is not flat and smooth. Islands and holes are formed on the free surface of the films when a sufficiently flat substrate is used. The thin film surface topography depends strongly on the nature of the bare substrate, the curing conditions, and the immersion time of the substrate in the DMOAP solution. The film is always rougher than the bare substrate used. Annealing roughens the surface of the alkoxysilane thin films deposited on a glass substrate. For films on glass plates covered with an indium tin oxide layer, annealing has minor effects. The surface topography affects the microstructure of homeotropic smectic samples.     

The influence of Ti plasma etching pre-treatment on mechanical properties of DLC film on cemented carbide

The pre-treatment of substrate surface had been a key part of DLC film preparation to improve mechanical and tribological properties. Ti plasma etching pre-treatment was investigated in this paper as a new effective surface pre-treatment method to substitute transition layer. This pre-treatment used high-energy Ti plasma to impact substrate surface. Ti plasma etched the substrate to a depth of 407 nm and increased the roughness from 1.36 to 40.39 nm. A trace layer of substrate, together with cobalt, oxides, and other impurities, was removed. Ti plasma broke some top WC crystals and combined with the free carbon ions separating from the substrate. A DLC film was deposited on the etched surface. Compared with DLC films deposited on the untreated substrate and Ti transition layer, the DLC film on the Ti plasma etched substrate had best adhesion strength of 34.14 N. The three DLC films had the same sp³ bonding carbon content, but Ti plasma etching treatment could promote the formation of sp³ bonds on the interface of substrate and DLC film. This DLC film had low friction coefficient of 0.12 and low wear rate of 5.11 × 10⁻⁷ mm³/m·N. In summary, Ti plasma etching pre-treatment could significantly improve the adhesion of DLC film and keep its excellent tribological properties.     

X-ray study of substrate-induced alignment of a smectic A liquid crystal

Abstract

We have performed a structural study of the liquid crystal (LC) octylcyanobiphenyl (8CB), deposited on gratings and flat surfaces, using high resolution X-ray scattering as a function of film thickness. 8CB is a room temperature smectic A₂, with a layer spacing of 31·6 Å. Glass was used as substrate and treated with either one of the organic surfactants MAP or DMOAP. Surface tension forces cause the liquid crystal molecules to align perpendicularly with respect to the plane of the substrate at the air interface. Competing with the LC-air interface, which is a strong aligner, a grating at the LC-substrate interface produces distortions in the smectic layering with an excess of elastic energy, which favours alignment parallel to the substrate and the grooves. Our purpose was to detect the onset and evolution of parallel alignment as a function of film thickness. The studies used 9 keV (1·403 Å) X-rays focused to a spot size of 2 mm² at the sample position. In-plane scans, which detect the smectic layers perpendicular to the plane of the substrate, were done at angles φ = 0° and 90° with respect to the gratings to ascertain the molecular orientation, at a nominal X-ray incidence angle of α = 0°. In order to observe regions of varying smectic layer orientation within the film, we performed a series of scans where the out-of-plane tilt angle χ changed from 0°, corresponding to scattering in the plane of the film, to 90°, which corresponds to scattering normal to the surface of the film. The results from these scans were fitted to a multilayer model where the orientation of the smectic layers varies as a function of film depth. The analysis confirmed our earlier observations that surface tension at the air interface plays a dominant role in the alignment of the LC molecules.     

Controlled nitroxide-mediated styrene surface graft polymerization with atmospheric plasma surface activation

Polymer layer growth by free radical graft polymerization (FRGP) and controlled nitroxide-mediated graft polymerization (NMGP) of polystyrene was achieved by atmospheric pressure hydrogen plasma surface activation of silicon. Kinetic polystyrene layer growth by atmospheric pressure plasma-induced FRGP (APPI-FRGP) exhibited a maximum surface-grafted layer thickness (125 A after 20 h) at an initial monomer concentration of [M] 0 = 2.62 M at 85 degrees C. Increasing both the reaction temperature ( T = 100 degrees C) and initial monomer concentration ([M] 0 = 4.36 M) led to an increased initial film growth rate but a reduced polymer layer thickness, due to uncontrolled thermal initiation and polymer grafting from solution. Controlled atmospheric pressure plasma-induced NMGP (APPI-NMGP), using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), exhibited a linear increase in grafted polystyrene layer growth with time due to controlled surface graft polymerization as well as reduced uncontrolled solution polymerization and polymer grafting, resulting in a polymer layer thickness of 285 A after 60 h at [TEMPO] = 10 mM, [M] 0 = 4.36 M, and T = 120 degrees C. Atomic force microscopy (AFM) surface analysis demonstrated that polystyrene-grafted surfaces created by APPI-NMGP exhibited a high surface density of spatially homogeneous polymer features with a low root-mean-square (RMS) surface roughness ( R rms = 0.36 nm), similar to that of the native silicon surface ( R rms = 0.21 nm). In contrast, polymer films created by APPI-FRGP at [M] 0 = 2.62 M demonstrated an increase in polymer film surface roughness observed at reaction temperatures of 85 degrees C ( R rms = 0.55 nm) and 100 degrees C ( R rms = 1.70 nm). The present study concluded that the current approach to APPI controlled radical polymerization may be used to achieve a grafted polymer layer with a lower surface roughness and a higher fractional coverage of surface-grafted polymers compared to both conventional FRGP and APPI-FRGP.     

Surface structure of amorphous PMMA from SPM: auto‐correlation function and fractal analysis

The surface topography of amorphous poly(methyl methacrylate) has been investigated by scanning probe microscopy technique and analysed using an auto‐correlation function approach. Spatial correlations in the arrangement of sub‐macromolecular fragments on the surface are studied depending on preparation conditions (whether the surface was free, i.e. in contact with air, or confined with the silicon substrate). The correlation length of the roughness distribution on the surface of amorphous polymers corresponds to the internal dimensions of unperturbed polymer chains (the radius of gyration). The scaling behaviour of the roughness is analysed with the Hurst approach, and found to be different for the free surface and for the confined one. As a result of annealing at a temperature above the glass transition temperature of the bulk polymer, both surfaces converge to similar fractal dimensionalities and correlation lengths.     

Diffusion,evaporation, and surface enrichment of a plasticizing additive in an annealed polymer thin film

We present the first measurements of the simultaneous diffusion, surface enhancement, and evaporation of a plasticizer from a polymer, thin-film matrix using neutron reflection techniques. The reflectivity profiles as a function of the annealing time at an elevated temperature yield the time-dependent, plasticizer volume fraction profiles in a polyester–polyurethane (Estane) film. Thin, plasticizer-enriched layers form at both the polymer/substrate and polymer/air interfaces for annealed and unannealed samples. The diffusion equations for a material diffusing through a film and then evaporating into a vacuum at the free surface describe the loss of the plasticizer from the film for annealed samples. The loss of the plasticizer from the film is not limited by the movement of the plasticizer through the polymer matrix but is dominated by the plasticizer's rate of evaporation from the surface. The rate of evaporation and the volume fraction profiles for the plasticizer at the substrate interface are both consistent with surface attractions dominating over bulk attractions between the miscible plasticizer and the polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3258–3266, 2004     

Lubrication, adsorption, and rheology of aqueous polysaccharide solutions

Aqueous lubrication is currently at the forefront of tribological research due to the desire to learn and potentially mimic how nature lubricates biotribological contacts. We focus here on understanding the lubrication properties of naturally occurring polysaccharides in aqueous solution using a combination of tribology, adsorption, and rheology. The polysaccharides include pectin, xanthan gum, gellan, and locus bean gum that are all widely used in food and nonfood applications. They form rheologically complex fluids in aqueous solution that are both shear thinning and elastic, and their normal stress differences at high shear rates are found to be characteristic of semiflexible/rigid molecules. Lubrication is studied using a ball-on-disk tribometer with hydrophobic elastomer surfaces, mimicking biotribological contacts, and the friction coefficient is measured as a function of speed across the boundary, mixed, and hydrodynamic lubrication regimes. The hydrodynamic regime, where the friction coefficient increases with increasing lubricant entrainment speed, is found to depend on the viscosity of the polysaccharide solutions at shear rates of around 10(4) s(-1). The boundary regime, which occurs at the lowest entrainment speeds, depends on the adsorption of polymer to the substrate. In this regime, the friction coefficient for a rough substrate (400 nm rms roughness) is dependent on the dry mass of polymer adsorbed to the surface (obtained from surface plasmon resonance), while for a smooth substrate (10 nm rms roughness) the friction coefficient is strongly dependent on the hydrated wet mass of adsorbed polymer (obtained from quartz crystal microbalance, QCM-D). The mixed regime is dependent on both the adsorbed film properties and lubricant's viscosity at high shear rates. In addition, the entrainment speed where the friction coefficient is a minimum, which corresponds to the transition between the hydrodynamic and mixed regime, correlates linearly with the ratio of the wet mass and viscosity at ～10(4) s(-1) for the smooth surface. These findings are independent of the different polysaccharides used in the study and their different viscoelastic flow properties.     

Roughness correlation and interdiffusion in thin films of polymer chains

The surface morphology of thin bilayer polymer films on top of glass substrates was investigated. The bilayer consists of a blend film of protonated and deuterated polystyrene and an underlying deuterated polystyrene film. Choosing the thickness of the top film larger than 8 times and smaller than 2 times the radius of gyration of the chains enables the determination of film thickness and confinement effects. With diffuse neutron scattering at grazing incidence in the region of total external reflection, a depth sensitivity and a contrast even at the internal polymer–polymer interface was achieved. The underlying film is conformal to the substrate, and depending on the thickness of the top film two different types of roughness correlations are observed. Thin confined films nestle to the underlying polymer films, while the stiffness of thicker bulky films provides an independent morphology. In both cases, annealing above the glass-transition temperature yields an interdiffusion at the internal polymer–polymer interface, and the polymer–air surface remains essentially unchanged with respect to roughness correlations. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2862–2874, 1999     

Layered self-organized structures on poly(3-octylthiophene) thin films studied by scanning probe microscopy

The morphology and mechanical properties of poly-(3-octylthiophene) P3OT films thin has been studied by scanning force microscopy techniques. On these films we find self-assembled layered structures that appear regardless of the preparation conditions, that is, spin-coating or drop-casting, of the solvent concentration or of the type of substrate. Using the drop-casting method for sample preparation these layered structures are hardly visible due to the high surface roughness, while using spin-coating these structures are the main topographic feature on the surface. These structures have typically one or two layers, even though occasionally up to four layers have been observed. Each layer has a height of 4-5 nm, which is associated to crystalline P3OT domains and lay on the polymer film. The size of these structures increases with increasing concentration of the P3OT in the solvent. We find well differentiated morphological, electrostatic as well as mechanical properties for the self-assembled structures as compared to the rest of the polymer film. Finally, the growth rate of these structures has been studied.     

Nanostructured ion-conductive films: Layered assembly of a side-chain liquid-crystalline polymer with an imidazolium ionic moiety

An ion-conductive mesogenic monomer with an imidazolium ionic moiety has been designed to obtain self-assembled materials forming ionic layers. Self-standing polymer films are prepared by in situ photopolymerization of the monomer that forms homeotropic monodomain on a normal glass substrate in the smectic A phase. Macroscopically oriented, layered nanostructures are formed in the film. The ionic conductivity parallel to the smectic layer has been measured for the oriented film. In the smectic A phase at 150 °C, the magnitude of conductivity is about 10⁻² S cm⁻¹. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3486–3492, 2003     

Wetting-dewetting transition line in thin polymer films

Thin polymeric films are increasingly being utilized in diverse technological applications, and it is crucial to have a reliable method to characterize the stability of these films against dewetting. The parameter space that influences the dewetting of thin polymer films is wide (molecular mass, temperature, film thickness, substrate interaction) and a combinatorial method of investigation is suitable. We thus construct a combinatorial library of observations for polystyrene (PS) films cast on substrates having orthogonal temperature and surface energy gradients and perform a series of measurements for a range of molecular masses (1800 g/mol < M < 35 000 g/mol) and film thicknesses h (30 nm < h < 40 nm) to explore these primary parameter axes. We were able to obtain a near-universal scaling curve describing a wetting-dewetting transition line for polystyrene films of fixed thickness by introducing reduced temperature and surface energy variables dependent on M. Our observations also indicate that the apparent polymer surface tension gamma(p) becomes appreciably modified in thin polymer films from its bulk counterpart for films thinner than about 100-200 nm, so that bulk gamma(p) measurements cannot be used to estimate the stability of ultrathin films. Both of these observations are potentially fundamental for the control of thin film stability in applications where film dewetting can compromise film function.     

Thickness and temperature‐dependent study of Co/Si interface

Thin films of cobalt (10, 40, and 100 nm) are deposited on Si substrate by electron beam physical vapor deposition technique. After deposition, 4 pieces from each of the wafers of silicon substrate were cut and annealed at a temperature of 200°C, 300°C, and 400°C for 2 hours each, separately. X‐ray diffraction, atomic force microscopy, and transmission electron microscopy (TEM) are used to study the structural and morphological characteristics of the deposited films. To obtain TEM images, Co films are deposited on Cu grids; so far, no such types of TEM images of Co films are reported. Structural studies confirm nanocrystalline nature with hexagonal close packed structure of the deposited Co film at lower thickness, while at higher thickness, film structure transforms to amorphous with lower surface roughness value. The particle sizes in all the cases are in the range of 3 to 5 nm. Micro‐Raman spectroscopy is also used to study the phase formation and chemical composition as a function of thickness and temperature. The results confirm that the grown films are of good quality and free from any impurity. Studies show the silicide formation at the interface during deposition. The appearance of new band at 1550 cm⁻¹ as a result of annealing indicates the structural transformation from CoSi to CoSi₂, which further enhances at higher annealing temperatures.     

Characteristics of thin cellulose ester films spin-coated from acetone and ethyl acetate solutions

Spin-coated films of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) have been characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The films were spin-coated onto silicon wafers, a polar surface. Mean thickness values were determined by means of ellipsometry and AFM as a function of polymer concentration in solutions prepared either in acetone or in ethyl acetate (EA), both are good solvents for the cellulose esters. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology, surface roughness and surface wettability were also investigated. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Free surface-induced bilayer smectic A phase in polar liquid crystals

Here the influence of the free surface on both a thick (semi-infinite) layer and a thin freely suspended film of a polar liquid crystal is investigated. It is shown that within the temperature range of the monolayer smectic A phase (S_A1) the interaction between polar molecules and the free surface of the liquid crystal gives rise to a bilayer smectic A, a structure with long range antiferroelectric order (S_A2) in the surface region of the semi-infinite layer. The dependence of the bilayer smectic order parameter on the strength of the interaction between the constituent molecules and the free surface as well as temperature and the distance to the free surface are determined. Sufficiently far from the S_A1-S_A2 transition the latter dependence has an exponential character and the depth of the S_A2 phase penetration into bulk liquid crystal is equal to the longitudinal correlation length for the bilayer smectic A structure fluctuations in the S_A1 phase. However, near the S_A1-S_A2 transition the bilayer smectic order parameter decays non-exponentially and more rapidly with increasing distance to the free surface. In addition, it is found that the bilayer S_A2 phase can form several smectic layers at the free surface of a semi-infinite polar liquid crystal layer with the S_A1 phase. Finally, it is shown that in a freely suspended film the free surface-induced S_A2 phase can completely occupy the volume of the sample. Hence in a freely suspended polar liquid crystal film the S_A1-S_A2 transition occurs with decreasing film thickness.     

Fabrication and characterization of superhydrophobic silica nanotrees

Superhydrophobic silica nanotrees were obtained by sol–gel method with hybrid silica sol and jelly-like resorcinol formaldehyde resin. Rough surfaces were obtained by removing the organic polymer at high temperature. After the films with rough surface were modified by trimethylchlorosilane (TMCS), the wettability of the film changed from superhydrophilic to superhydrophobic. The surface roughness of the silica nanotrees film is about 20 nm, and it is transparent and superhydrophobic with a water contact angle higher than 150°.     

Modified polymer substrates for the formation of submicron particle ensembles from colloidal solution

Methods for targeted regulation of the surface properties of polymer film materials (substrates) by fluorination and sulfonation have been considered. It has been shown by the examples of polyethylene, polypropylene, and poly(ethylene terephthalate) films that these methods can be used for the production of polymer films with controlled values of water contact angle from 20° to 88°, adhesion force from 23 to 141 rel. units, and surface roughness parameter R_a from 35 to 382 nm. This set of substrates may be used to optimize the methods for the formation of structured functional polymer surfaces. In particular, the regularities of the formation of solid deposits of colloidal submicron particles during evaporation of droplets of their solutions have been shown to vary with variations in substrate characteristics.     

Nanometer scale characterization of polymer films by atomic-force microscopy

Atomic-force microscopy was applied to perform a comprehensive surface roughness characterization of commercially available, highly transparent polymer films for transparent insulation applications. The morphological characterization included evaluation of the root-mean-square roughness, the lateral correlation length of roughness as well as the roughness exponent. In addition, high-resolution scans have been recorded yielding morphological information on a length scale of only a few ten nm. These measurements revealed the correlation between surface nanostructure and fabrication technique. For an impact-modified polymethylmethacrylate film with rubber inclusions phase images clearly uncovered the core-shell structure of these inclusions.