Cellulose Thin Films Research Articles

Fabrication of a model cellulose surface from straw with an aqueous sodium hydroxide/thiourea solution

AbstractModel cellulose surfaces were prepared with both microcrystalline cellulose and cellulose isolated from wheat straw with different molecular weights. A sodium hydroxide/thiourea aqueous solution, instead of any organic solvents, worked as the solvent for dissolving cellulose, and model cellulose films were prepared by a two‐step method: first, the cellulose solution was deposited onto the surface of the substrate with the spin‐coating method, and second, the as‐prepared film was washed with deionized water to remove the impurities and was formed with a flattened surface. Atomic force microscopy was used to measure the morphology, surface roughness, and thickness of the cellulose thin films. X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray spectrometry were used to characterize the surface chemical information of the films. The results revealed that model cellulose surfaces could form from both kinds of cellulose. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Effect of introduced charge in cellulose gels on surface interactions and the adsorption of highly charged cationic polyelectrolytes

The interaction between cellulose surfaces in aqueous solution has been measured using colloidal probe microscopy. Cellulose thin films with varying charge through carboxyl group substitution were used in this study with the surface forces fit to DLVO theory. It was found that the surface potential increased, as expected, with increasing carboxyl substitution. Furthermore, for a given degree of substitution, the surface potential increased as a function of increasing pH. At low pH, the surface forces interaction were attractive and could be fit to the non-retarded Hamaker equation using a constant of 3 x 10(-21) J. At pH greater than 5, the force interactions were monotonically repulsive, regardless of the ionic strength of the solution for all charge densities of the cellulose thin films. The adsorption of polyDADMAC to these charged cellulose films was also investigated using the quartz crystal microbalance. It was found that for the low charge film, a low surface excess of PDADMAC was sensed and that the adsorbed conformation was essentially flat. However for the higher charged cellulose film, a spontaneous de-swelling was observed resulting in no possibility of quantitatively determining the sensed mass using QCM.

Surfactant Adsorption onto Cellulose Surfaces

The adsorption of the cationic surfactant, hexadecyl trimethyl ammonium bromide, C16TAB, onto model cellulose surfaces, prepared by Langmuir-Blodgett deposition as thin films, has been investigated by neutron reflectivity. Comparison between the adsorption of C16TAB onto hydrophilic silica, a hydrophobic cellulose surface, and a regenerated (hydrophilic) cellulose surface is made. Adsorption onto the hydrophilic silica and onto the hydrophilic cellulose surfaces is similar, and is in the form of surface aggregates. In contrast, the adsorption onto the hydrophobic cellulose surface is lower and in the form of a monolayer. The impact of the surfactant adsorption and the in situ surface regeneration on the structure of the cellulose thin films and the nature of solvent penetration into the cellulose films are also investigated. For the hydrophobic cellulose surface, intermixing between the cellulose and surfactant occurs, whereas there is little penetration of surfactant into the hydrophilic cellulose surface. Measurements show that solvent exchange between the partially hydrated cellulose film and the solution is slow on the time scale of the measurements.

Cellulose Thin Films: Degree of Cellulose Ordering and Its Influence on Adhesion

Adhesion measurements have been performed with thin cellulose films using continuum contact mechanics with application of the JKR theory. Three different cellulose surfaces were prepared, one crystalline and two surfaces with a lower degree of crystalline order. Adhesion between two cross-linked poly(dimethylsiloxane) (PDMS) caps, as well as the adhesion between PDMS and the various cellulose surfaces, was measured. The work of adhesion (from loading) was found to be similar for all three surfaces, and from contact angle measurement with methylene iodide it was concluded that dispersive interactions dominate. However, the adhesion hysteresis differed significantly, being larger for a less ordered cellulose surface and decreasing with increasing degree of crystalline order. This is suggested to be due to the surface groups' ability to orient themselves and participate in specific or nonspecific interactions, where a surface with a lower degree of crystalline order has a higher possibility for reorientation of the surface groups. The mobility of cellulose chains increases with water uptake, resulting in stronger adhesive joints. These films will hence allow for determination of the contributions of hydrogen bonding and inter-diffusion on the adhesion, determined from the unloading data, as the thermodynamic work of adhesion was found to be independent of the cellulose surface used.

Charging and swelling of cellulose films

Charging and swelling of cellulose in aqueous environments are of highest interest with respect to the performance of cellulose based products and applications. To unravel the interplay between ionization and structural features of the biopolymer hydrogel we compared non-crosslinked and crosslinked cellulose thin films based on a determination of the Donnan potential [S.S. Dukhin, R. Zimmermann, C. Werner, J. Colloid Interface Sci. 274 (2004) 309] from microslit electrokinetic (streaming potential/streaming current) experiments and layer thicknesses from ellipsometry in aqueous electrolyte solutions. The pH dependence of the Donnan potential, reflecting the ionization of carboxylic acid groups within the cellulose films, was found to be significantly different from the related trend of the streaming current which reflects the characteristics of the topmost surface of the layers: While carboxylic acid groups on the surface of the films dissociate as isolated functionalities, the electrostatic interactions of ionized groups within the cellulose layers cause an incomplete dissociation (p K shift) of the carboxylic acid and a layer expansion (swelling) in the alkaline pH range. The system was found to restrict its volume charge density even after structural restrictions (crosslinking) of the layer and at lower ionic strength of the solutions through a further decrease of the degree of dissociation of the carboxylic acid functions. These findings were attributed to the local accumulation of the carboxylic acid groups caused by preferential oxidation of the amorphous regions of the cellulose and to the ordered water structure within the layer.

Electro-deposition of thin cellulose films at boron-doped diamond substrates

Cellulose films of variable thickness are electro-deposited from aqueous alkaline thiourea solution onto polished boron-doped diamond substrates in an anodic process. Films with “net-like” topography are formed and shown to consist of both cellulose-I and cellulose-II components. Properties of these films are investigated. When immersed in aqueous electrolyte solution, ion partitioning into the electro-deposited cellulose films occurs. The accumulation and release of two aqueous redox systems, Ru ( NH 3 ) 6 3 + / 2 + and methylviologen 2+/+, is reported. Relatively slow diffusion of these cations is observed within cellulose (approximately 5 orders of magnitude slower when compared to diffusion in aqueous media). For the methylviologen 2+/+ redox system partitioning leads to irreversibility in the voltammetric response and to the preferred formation of aggregates immobilized within the cellulose film.

Determination of menthol kinetic constants with Love-wave device

Love-wave devices gained enormous interest for sensor applications which need real time analyses and high sensitivity. These devices proved to be suitable for sensing physical quantities like mass. This effect is known as the main sensing mechanism in acoustic sensors and thanks to their high sensitivity, Love-wave can detect a small mass loading on the surface of the acoustic propagation medium. In this study, we present a new method to characterize in quasi real time evaporation of volatile compounds instead of several weeks for current experiments. A Love-wave device is used to determine menthol evaporation kinetic constant when menthol is associated with a polymer called ethyl cellulose (EC). For that, menthol and ethyl cellulose mixture were deposited as sensitive coating with a spray coating system. Experiments consisted in recording of frequency shifts during deposition of menthol and ethyl cellulose thin film. The evaporation of the volatile compound was followed in real time through mass variations of the film. A fit of the Love-wave sensor response allowed to determine characteristic constants associated to the evaporation kinetic of volatile compound in a few minutes.

Effect of Lumophore and Plasticiser Concentration on The Heterogeneity of Oxygen Quenching in Thin Film Oxygen Sensors

Kinetic heterogeneity of the luminescence decay and oxygen quenching of Pt and Pd octaethylporphyrin/ethyl cellulose (OEP/EC) thin film oxygen sensors has been investigated with respect to (a) concentration of lumophore and (b) addition of plasticiser. The source of kinetic heterogeneity shown by PtOEP films under N2 is a monomer-dimer equilibrium in which the dimer luminescence decays with k = 0.0527 x 10(6) s(-1) and the monomer luminescence with k = 0.0101 x 10(6) s(-1) and KD = 790 (+/-20) mol dm(-3). For PdOEP/EC films there is no detectable aggregation and luminescence decays under N2 show good fits to single exponential curve fits at all concentrations studied. The addition of either tripbutyl phosphate or dimethylphthalate as plasticiser does not decrease kinetic heterogeneity for oxygen quenching of luminescence in the films.

Surface Forces Measurements of Spin-Coated Cellulose Thin Films with Different Crystallinity

A systematic study of the surface forces between a cellulose sphere and cellulose thin films of varying crystallinity has been conducted as a function of ionic strength and pH. Semicrystalline cellulose II surfaces and amorphous cellulose films were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose I nanocrystals. These preparation methods produced thin, smooth films suitable for surface forces measurements. The interaction with the cellulose I was monotonically repulsive at pH 3.5, 5.8, and 8.5 and at 0.1, 1, and 10 mM ionic strengths. This was attributed to the presence of strongly ionizable sulfur-containing groups on the cellulose nanocrystal surfaces. The amorphous film typically showed a steric interaction up to 100 nm away from the interface that was independent of the solution conditions. A range of surface forces were successfully measured on the semicrystalline cellulose II films; attractive and repulsive regimes were observed, depending on pH and ionic strength, and were interpreted in terms of van der Waals and electrostatic interactions. Clearly, the forces acting near cellulose surfaces are very dependent on the way the cellulose surface has been prepared.

Covalent Immobilization of Cellulose Layers onto Maleic Anhydride Copolymer Thin Films

Thin films of cellulose are advantageous for analytical studies in aqueous environments to investigate various factors determining the performance of cellulose-based products. However, the weak fixation of cellulose layers on common carrier materials often limits this approach. To address this problem, we suggest a novel maleic anhydride copolymer precoating technique which allows for the covalent attachment of cellulose thin films through esterification. Maleic anhydride copolymers were deposited and covalently bound onto planar, aminosilane-modified glass or silicon oxide surfaces. Cellulose was subsequently immobilized on top of the copolymer precoatings by spin coating from N-methylmorpholine-N-oxide/dimethyl sulfoxide solutions. The resulting cellulose films were thoroughly characterized with respect to layer thickness, morphology, chemical constitution, and electrical charging. The stability of the layers against shear stress was demonstrated in aqueous solutions and the covalent attachment of the cellulose to the copolymer films was proven by means of dissolution experiments followed by ellipsometry and high-resolution X-ray photoelectron spectroscopy.

Interaction forces between cellulose microspheres and ultrathin cellulose films monitored by colloidal probe microscopy—effect of wet strength agents

Colloidal probe microscopy was employed to study forces between cellulose surfaces upon addition of a series of cationic copolymers in aqueous solution, as model compounds for wet strength agents. The content of quaternary ammonium groups and primary amines was systematically varied in the cationic polymers, to distinguish between the importance of electrostatical and H-bonding effects. Cellulose microspheres were glued at the apex of tipless microfabricated cantilevers and used as colloidal probes. Ultra thin cellulose films and cellulose fibres were employed as model surfaces. The cellulose films of a thickness of about 5 nm were spin-coated from cellulose solution onto silicon substrates. The root-mean-square-roughness (RMS) was 0.3-0.8 nm. The cationic model polymers were compared to Servamine, a polymer employed as standard wet strength resin in papermaking industries. Force versus separation measurements showed a detailed picture of adhesion and contact breaking. Relatively strong adhesion of the order of 0.3 mJ/m(2) was observed with Servamine within a range of approximately 10 nm. At larger distances weak bond breaking and elastic chain pulling were identified. When approaching the surface one to two small jump-in's possibly related to strong binding of Servamine and subsequent attraction could be found in the case of Servamine. In contrast, all the model copolymers showed only a weak adhesion of 8-30 micro/m(2), i.e., an order of magnitude less than that of Servamine and subsequent elastic rupture domains. The contour length, persistence length and characteristic rupture distances were calculated by means of applying the WLC model. Measurements against cellulose fibres obtained from the production process proved the relevance of the model systems.

Production of bioactive cellulose films reconstituted from ionic liquids.

A new method for introducing enzymes into cellulosic matrixes which can be formed into membranes, films, or beads has been developed using a cellulose-in-ionic-liquid dissolution and regeneration process. Initial results on the formation of thin cellulose films incorporating dispersed laccase indicate that active enzyme-encapsulated films can be prepared using this methodology and that precoating the enzyme with a second, hydrophobic ionic liquid prior to dispersion in the cellulose/ionic liquid solution can provide an increase in enzyme activity relative to that of untreated films, presumably by providing a stabilizing microenvironment for the enzyme.

Actual air separation across multilayer composite membranes

Multilayer composite membranes are fabricated from six types of thin films as selective layers, an ethyl cellulose (EC) thin film as a flexible spacer, and poly(ether sulfone) (PES) with 15–45 nm pore size or 100–120 μm thickness as a porous support layer. The effects of the thin-film type and its layer number, operating temperature, and transmembrane pressure difference, as well as the operational time on the actual air-separation properties through the composite membranes, are investigated by a constant pressure-variable volume method. The results show that a pure polystyrene thin-film composite membrane exhibits poor actual air-separation performance due to its brittleness, although it has a higher ideal oxygen over nitrogen separation factor. The oxygen-enrichment air (OEA) flux through all of the composite membranes tested increases significantly with increasing operating temperature and pressure difference. The oxygen concentration in the OEA increases slightly with an increase in operating temperature, and the oxygen concentration through the polystyrene/cholesteryl oleyl carbonate blend, top layer composite membrane exhibits the maximal value. As the transmembrane pressure difference increases, the oxygen concentration in the OEA also exhibits the maximal value. The maximum oxygen concentration can reach 39.1%, which is achieved by the multilayer composite membrane consisting of a polystyrene/cholesteryl oleyl carbonate (95/5) monolayer, an EC single flexible spacer, and a PES support at 35°C and a transmembrane pressure difference of 550 kPa. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2396–2403, 2000

Actual air separation across multilayer composite membranes

Multilayer composite membranes are fabricated from six types of thin films as selective layers, an ethyl cellulose (EC) thin film as a flexible spacer, and poly(ether sulfone) (PES) with 15–45 nm pore size or 100–120 μm thickness as a porous support layer. The effects of the thin-film type and its layer number, operating temperature, and transmembrane pressure difference, as well as the operational time on the actual air-separation properties through the composite membranes, are investigated by a constant pressure-variable volume method. The results show that a pure polystyrene thin-film composite membrane exhibits poor actual air-separation performance due to its brittleness, although it has a higher ideal oxygen over nitrogen separation factor. The oxygen-enrichment air (OEA) flux through all of the composite membranes tested increases significantly with increasing operating temperature and pressure difference. The oxygen concentration in the OEA increases slightly with an increase in operating temperature, and the oxygen concentration through the polystyrene/cholesteryl oleyl carbonate blend, top layer composite membrane exhibits the maximal value. As the transmembrane pressure difference increases, the oxygen concentration in the OEA also exhibits the maximal value. The maximum oxygen concentration can reach 39.1%, which is achieved by the multilayer composite membrane consisting of a polystyrene/cholesteryl oleyl carbonate (95/5) monolayer, an EC single flexible spacer, and a PES support at 35°C and a transmembrane pressure difference of 550 kPa. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2396–2403, 2000

Surfactant adsorption and water desorption on thin cellulose films monitored by in-situ ATR-FTIR spectroscopy

Surfactant adsorption and water desorption on thin cellulose films monitored by in-situ ATR-FTIR spectroscopy

Atomic force microscopy and high-resolution scanning electron microscopy study of the banded surface morphology of hydroxypropyl cellulose thin films

Low voltage high resolution SEM and atomic force microscopy (AFM) studies both indicate that a sinusoidal fibrillar morphology is associated with the banded texture observed in hydroxypropylcellulose thin films. The AFM studies clearly demonstrate that the fibrillar trajectory deviates from lying on the plane of shear, and for shear bands with 6 μm wavelength, this deviation was found to be ∼ 4-10°

Air Separation through Modified Ethyl Cellulose Thin Film Supported on Porous Polyethersulfone

Abstract Composite membranes for air separation were prepared from a liquid crystal DYC-modified ethyl cellulose (EC) thin film ranging in thickness from 1 to 7 μm and a porous polyethersulfone support with a thickness of 120 μm. The effects of DYC/EC (9/91) solution concentration, water, and operating parameters such as temperature, pressure, and time on the air-separation properties of the composite membranes were examined by a constant pressure—variable volume method. The permeate flux and oxygen concentration of the oxygen-enriched air (OEA) through the membranes increase significantly with increasing operating pressure difference. With decreasing casting solution concentration, or with increasing humidity around the membranes or operating temperature, the OEA flux increases greatly while the oxygen concentration sometimes decrease slightly. An increase in the operating time leads to an OEA flux decline, but the oxygen concentration rose when the operating time was varied for 70 hours. However, a further increase of the operating time from 70 to 500 hours does not lead to further changes of the OEA flux and oxygen concentrations. A thin-film composite membrane exhibits a slightly lower oxygen concentration accompanied by a very significant enhancement in the OEA flux and membrane stability compared to a homogeneous dense membrane of the same materials.

Ultrathin films of cellulose on silicon wafers

The first preparation of thin films of cellulose itself is reported. Cellulose exhibits excellent wetting behavior, is extremely stable against oxidation and other chemical degradation and in thin‐film form would have a number of applications. The method involves the preparation of LB films of trimethylcellulose (see Figure) and the in situ conversion of these thin films on silicon substrates to cellulose. magnified image

Effects of sorbed water on the dielectric constant of some cellulose thin films

Relation entre la constante dielectrique et l'humidite adsorbee pour de l'acetate de cellulose, de l'acetophtalate acide de cellulose, d'acetobutyrate de cellulose et d'ethylcellulose en vue de leur utilisation comme detecteur d'humidite

A new technique for studying the quantitative aspects of cytochemical reactions and its application to the Feulgen reaction.

QUANTITATIVE microspectrophotometry of cytochemically stained substances in cellular structures should be based on a knowledge of the stoichiometry of the reactions involved and the conditions influencing it. Thus far independent chemical analysis of individual cellular structures to study the quantitative relation between colour and amount of stained substance in general is not possible. This relation can be studied on a macro-scale by incorporating the substance in a kind of artificial section or model system which makes it possible to carry out the staining procedure under cytochemical conditions. For this purpose thin cellulose films were chosen. The extinction of the film after the staining procedure is proportional to the mass of the stained substance per unit area in the film. This mass is proportional to the amount of cellulose in the same area, provided the substance is uniformly distributed.