Effect of humidity and solvent vapor phase on cellulose esters films

In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 ± 5)%, (55 ± 5)% or (75 ± 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 ± 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.     

Characterization of Ultrathin Films of Cellulose Esters

The adsorption of cellulose acetate (CA), cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from solutions prepared in acetone onto silicon wafers led to ultrathin films, which were characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The polysaccharides films were characterized in the air just after their formation and after annealing at temperatures higher than their glass transition temperature or melt temperature. The films thickness close to 2 nm and surface roughness did not vary significantly upon annealing. AFM images revealed the presence of small clumps dispersed on a homogeneous layer, which covered completely the Si wafers. Such topographic details were also observed after annealing. However, upon annealing the films surfaces changed from hydrophilic to hydrophobic, evidencing molecular re-orientation at the solid–air interface. The adhesion of bovine serum albumin (BSA) and lipase onto the cellulose esters films was quantified in order to evaluate the possibility of applying such films as selective support for biomolecules.     

Stability of monomolecular films of archaebacterial tetraether lipids on silicon wafers: a comparison of physisorbed and chemisorbed monolayers

The monomolecular organisation of symmetric, chemically modified tetraether lipids caldarchaeol-PO(4) was studied using Langmuir film balance, ellipsometry, and atomic force microscopy (AFM). Solid silicon wafer substrates were modified to hydrophobic, hydrophilic, and amino-silanised surfaces; and Langmuir-Blodgett (LB)-films were transferred onto each. LB-caldarchaeol-PO(4) films were subjected to further rinsing with organic solvent and additional physical treatments, to compare their resistance and stability on chemisorbed (amino-silanised) and physisorbed (hydrophobic and hydrophilic) surfaces. The resistance and stability of these monolayer films was characterized by ellipsometry and AFM, and film thickness was determined using ellipsometry. AFM was also employed to observe surface morphology. Monolayer films on hydrophobic surfaces were found to be more resistant to rinsing with organic solvent and additional physical treatments than monolayer films on either amino-silanised or hydrophilic surfaces. The hydrophobic effect with hydrophobic surfaces appears to support the formation of stronger caldarchaeol-PO(4) films on silicon wafer substrates, with increased resistance and stability.     

Multi-technique surface characterization of bio-based films from sisal cellulose and its esters: a FE-SEM, μ-XPS and ToF-SIMS approach

Bio-based films were prepared from LiCl/DMAc solutions containing sisal cellulose esters (acetates, butyrates and hexanoates) with different degrees of substitution (DS 0.7–1.8) and solutions prepared with the cellulose esters and 20 wt% sisal cellulose. A novel approach for characterizing the surface morphology utilized field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and contact angle analysis. XPS and ToF-SIMS were a powerful combination while investigating both the ester group distribution on the surface and effects of cellulose content on the film. The surface coverage by ester aliphatic chains was estimated using XPS measurements. Fibrous structures were observed in the FE-SEM images of the cellulose and bio-based films, most likely because the sisal cellulose chains aggregated during dissolution in LiCl/DMAc. Therefore, the cellulose aggregates remained after the formation of the films and removal of the solvent. The XPS results indicated that the cellulose loading on the longer chain cellulose esters films (DS 1.8) increased the surface coverage by ester aliphatic chains (8.2 % for butyrate and 45 % for hexanoate). However, for the shortest ester chains, the surface coverage decreased (acetate, 42 %). The ToF-SIMS analyses of cellulose acetate and cellulose hexanoate films (DS 1.8) revealed that the cellulose ester groups were evenly distributed across the surface of the films.     

Comparative characterisation by atomic force microscopy and ellipsometry of soft and solid thin films

Ellipsometry and atomic force microscopy (AFM) were used to study the film thickness and the surface roughness of both ‘soft’ and solid thin films. ‘Soft’ polymer thin films of polystyrene and poly(styrene–ethylene/butylene–styrene) block copolymer were prepared by spin‐coating onto planar silicon wafers. Ellipsometric parameters were fitted by the Cauchy approach using a two‐layer model with planar boundaries between the layers. The smooth surfaces of the prepared polymer films were confirmed by AFM. There is good agreement between AFM and ellipsometry in the 80–130 nm thickness range. Semiconductor surfaces (Si) obtained by anisotropic chemical etching were investigated as an example of a randomly rough surface. To define roughness parameters by ellipsometry, the top rough layers were treated as thin films according to the Bruggeman effective medium approximation (BEMA). Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased etching time, although AFM results depend on the used window size. The combined use of both methods appears to offer the most comprehensive route to quantitative surface roughness characterisation of solid films. Copyright © 2007 John Wiley & Sons, Ltd.     

Catalytic activity of lipase immobilized onto ultrathin films of cellulose esters

Ultrathin (approximately 2.0 nm) films of cellulose acetate (CA), cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB) supported on Si wafers have been prepared by adsorption and characterized by means of ellipsometry, atomic force microscopy (AFM), and contact angle measurements. CA, CAP, and CAB ultrathin films were characterized in air just after their formation and after annealing under reduced pressure at temperature higher than the corresponding melt temperature. Upon annealing, CA, CAP, and CAB ultrathin films became smoother and more hydrophobic, evidencing molecular reorientation at the solid-air interface. CA, CAP, and CAB films were used as supports for the immobilization of lipase. The adsorption of lipase onto annealed films was more pronounced than that onto untreated films, showing the strong affinity of lipase for the more hydrophobic substrates. Enzymatic activity was evaluated by a standard procedure, namely, (spectrophotometric) measurement of p-nitrophenol, the product formed from the hydrolysis of p-nitrophenyl dodecanoate (p-NPD). Lipase immobilized onto hydrophobic films exhibited higher activity than that of free lipase and could be recycled three times while retaining relatively high activity (loss of ca. 30% of original enzymatic activity). The effect of storing time on the activity of immobilized lipase was studied. Compared with free lipase, that immobilized onto more hydrophobic films retained 70% activity after 1 month. More importantly, the latter level of activity is similar to that of free lipase. However, lipase immobilized onto more hydrophilic films retained 50% and 30% activity after 20 and 30 days, respectively. These results are explained in terms of surface wettability and the contribution of the interactions between the polar residues of lipase and the glucopyranosyl moieties of cellulose ester to maintain the natural conformation of immobilized enzyme.     

Porous structures of polymer films prepared by spin coating with mixed solvents under humid condition

We investigate the effects of interfacial energy between water and solvent as well as polymer concentration on the formation of porous structures of polymer films prepared by spin coating of cellulose acetate butyrate (CAB) in mixed solvent of tetrahydrofuran (THF) and chloroform under humid condition. The interfacial energy between water and the solvent was gradually changed by the addition of chloroform to the solvent. At a high polymer concentration (0.15 g/cm3 in THF), porous structures were limited only at the top surfaces of CAB films, regardless of interfacial energies, due to the high viscosity of the solution. At a medium concentration (approximately 0.08 g/cm3 in THF), CAB film had relatively uniform pores at the top surface and very small pores inside the film because of the mixing of the water droplets with THF solution. When chloroform was added to THF, pores at the inner CAB film had a comparable size with those at the top surface because of the reduced degree of the mixing between the water droplets and the mixed solvent. A further decrease in polymer concentration (0.05 g/cm3 in THF) caused the final films to have a two-layer porous structure, and the size of pores at each layer was almost the same.     

Covalent molecular assembly of oligoimide ultrathin films in supercritical and liquid solvent media

An ultrathin film of oligoimide has been fabricated on amine-modified substrates of silicon and quartz through alternate layer-by-layer (LBL) assembly of pyromellitic dianhydride (PMDA) and diaminodiphenyl ether (DDE), with interlayer links established by covalent bonds. The assembly was formed in supercritical carbon dioxide (SCCO2) and in solution (dimethyl acetamide, DMAc), and the imidization reaction was performed by thermal and chemical methods, in benzene and in the supercritical medium. X-ray photoelectron and UV-visible absorption spectroscopies, atomic force microscopy (AFM), and ellipsometry were employed to study the interfacial chemistry, growth, morphology, and thickness of the assembled film. XPS analysis confirmed the sequential deposition of PMDA and DDE through formation of amic acids. At each deposition step, surface functionalities for the assembly of the next layer were generated. The interfacial chemical reaction was almost complete in the SCF (supercritical fluid) medium, as compared to the conversions observed in conventional assembly. Both the PMDA and DDE molecules were assembled in an organized manner, resulting in uniform surface morphology. Uniform film growth was revealed from the increase of UV absorption intensity and film thickness. The overall growth and quality of the films in SCF medium were greater than that for films formed in DMAc. The results of this novel study show that an environmentally friendly solvent can be used to obtain mechanically robust and thermally stable ultrathin films with little loss of material during the imidization step. In contrast to conventional deposition of the molecular layers that utilizes liquid solvents, use of SCCO(2) avoids solvent effects and posttreatment for solvent removal, while ensuring facile transport during contact.     

Enzymatic degradation of model cellulose films

Enzymatic degradation of model cellulose films prepared by a spin-coating technique was investigated by ellipsometry. The cellulose films were prior to degradation characterized by ellipsometry, contact angle measurements, ESCA (electron spectroscopy for chemical analysis) and AFM (atomic force microscopy). At enzyme addition to preformed cellulose films an initial adsorption was observed, which was followed by a total interfacial mass decrease due to enzymatic degradation of the cellulose films. The degradation rate was found to be constant during an extended time of hours, whereafter the degradation leveled off. In parallel to the decreased interfacial mass, the cellulose degradation resulted in a thinner and more dilute interfacial film. At long degradation times, however, there was an expansion of the cellulose film. The enzyme concentration affected the degradation rate significantly, with a faster degradation at a higher enzyme concentration. The effects of pH, temperature, ionic strength and stirring rate in the cuvette were also investigated.     

Preparation and Characterization of 6-<Emphasis Type="Italic">O</Emphasis>-(4-stearyloxytrityl)Cellulose acetate Langmuir–Blodgett Films

Multilayer films of 2,3-di-O-acetyl-6-O-(4-stearyloxytrityl)cellulose (ASTC) were prepared and investigated. The fairly high surface pressure (π)–area (A) isotherms (36– 47 mN/m) suggest that the balky and hydrophobic trityl group contribute to form a condensed monolayer. The cellulose derivative formed a homogeneous monolayer at 10 mN/m. The monolayer on the water surface was transferred successfully at 10 mN/m onto various substrates by modifying the preparation methods, to form Z-type multilayer films. The ultraviolet–visible (UV–Vis) absorbance was independent of the number of layers, indicating that each layer is made of definite number of anhydroglucose unit (AGU). The monolayer thickness determined from atomic force microscope (AFM) and ellipsometry was calculated to be about 1.9 nm, suggesting that the long alkyl chain in the film has a so-called hairy-rod type structure. This is the first paper about the Z-type LB film prepared from cellulose derivatives having long mono-alkyl chain only at 6-O-position.     

Solvent impact on esterification and film formation ability of nanofibrillated cellulose

In this study we have manufactured nanofibrillar cellulose and modified the fibre surface with ester groups in order to hydrophobise the surface. Nanofibrillated cellulose was chosen to demonstrate the phenomena, since due to its high surface area the effects at issue are pronounced. The prepared NFC ester derivatives were butyrate, hexanoate, benzoate, naphtoate, diphenyl acetate, stearate and palmitate. X-ray photoelectron spectroscopy, solid state NMR and contact angle measurements were used to demonstrate the chemical changes taking place on the cellulose surface. NFC ester derivatives can be prepared after a careful solvent exchange to a water-free solvent medium has been carried out. Butyl and palmitoyl esters were chosen for film forming tests due to the difference in their carbon chain lengths, and their contact angles and water vapour and oxygen permeation rates were studied. The prepared nanocellulose esters show increased hydrophobicity even at very low levels of substitution and readily form films when the films are prepared from acetone dispersions. The permeation rates suggest a potential use as barrier materials.     

Dense passivating poly(ethylene glycol) films on indium tin oxide substrates

We describe the formation and characterization of surface-passivating poly(ethylene glycol) (PEG) films on indium tin oxide (ITO) glass substrates. PEG chains with a molecular weight of 2000 and 5000 D were covalently attached to the substrates in a systematic approach using different coupling schemes. The coupling strategies included the direct grafting with PEG-silane, PEG-methacrylate, and PEG-bis(amine), as well as the two-step functionalization with aldehyde-bearing silane films and subsequent coupling with PEG-bis(amine). Elemental analysis by X-ray photoelectron spectroscopy (XPS) confirmed the successful surface modification, and XPS and ellipsometry provided values for film thicknesses. XPS and ellipsometry thickness values were almost identical for PEG-silane films but differed by up to 400% for the other PEG layers, suggesting a homogeneous layer for PEG-silane but an inhomogeneous distribution for other PEG coatings on the molecularly rough ITO substrates. Atomic force microscopy (AFM) and water contact angle goniometry confirmed the different degrees of surface homogeneity of the polymer films, with PEG-silane reducing the AFM rms surface roughness by 50% and the water contact angle hysteresis by 75% compared to uncoated ITO. The ability of the PEG layers to passivate the substrate against the nonspecific adsorption of biopolymers was tested using fluorescence-labeled immunoglobulin G and DNA oligonucleotides in combination with fluorescence microscopy. The results indicate a positive relationship between film density and homogeneity on one hand and the ability to passivate against biopolymer adhesion on the other hand. The most homogeneous layers prepared with PEG-silane reduced the nonspecific adsorption of fluorescence-labeled DNA by a factor of 300 compared to uncoated ITO. In addition, the study finds that the ratio of film thicknesses derived by ellipsometry and XPS is a useful parameter to quantify the structural integrity of PEG layers on molecularly rough ITO surfaces. The findings may be applied to characterize PEG or other polymeric films on similarly coarse substrates.     

Solution behavior and surface properties of carboxymethylcellulose acetate butyrate

Solution behavior of carboxymethylcellulose acetate butyrate (CMCAB) in acetone and ethyl acetate has been investigated by small-angle X-ray scattering (SAXS) and capillary viscometry and correlated with the characteristics of CMCAB films. Viscosity and SAXS measurements showed that ethyl acetate is a better solvent than acetone for CMCAB. Thin films of CMCAB were deposited onto silicon wafers (Si/SiO₂) by spin coating. AFM images revealed that CMCAB spin coated films from solutions prepared in ethyl acetate were homogeneous and flat. However, films obtained from solutions in acetone were very rough. Contact angle measurements with polar and apolar test liquids characterized CMCAB surfaces as hydrophobic and allowed estimating the surface energy of CMCAB. Sum frequency generation vibrational spectroscopy was used to understand the role played by solvents and to gain insight about molecular orientation at Si/SiO₂/CMCAB interface.     

Morphological studies of spin-coated films of poly(styrene-block-methyl methacrylate) copolymers by atomic force microscopy

The surface structure of very thin (15–20 nm) spin-coated films of a symmetrical poly(styrene-b-methyl-methacrylate) block copolymer on silicon and mica is analyzed by atomic force microscopy (AFM). The films show a surface corrugation of a very regular 100 nm lateral periodicity and 6–8 nm amplitude. Film thickness is measured by AFM at induced film defects and checked by ellipsometry. XPS shows that both blocks are at the film surface. Selective degradation of the methyl methacrylate block is used for contrast enhancement and allows to assign poly(styrene) to the elevated surface regions and poly(methyl methacrylate) to the substrate/film interface.Friction interactions of the AFM tip with the film surface may be used to induce high orientational ordering of the morphological pattern perpendicular to the fast scan direction.     

Covalent molecular assembly of multilayer dendrimer ultrathin films in supercritical medium

Ultrathin films containing dendrimers are fabricated on amine- and anhydride-derivatized silicon dioxide surface through alternate layer-by-layer (LbL) assembly of pyromellitic dianhydride (PMDA) and poly(amidoamine) (PAMAM) dendrimer in supercritical carbon dioxide (SCCO2) with interlayer linkage established by covalent bonds. X-ray photoelectron and UV-visible absorption spectroscopies, atomic force microscopy (AFM), and ellipsometry were employed to study the interfacial chemistry, growth, morphology, and thickness of the assembled film. XPS analysis suggests that the PMDA/PAMAM interlayer covalent bond is established to completion, and functional surfaces for immobilization of the next layer are available after deposition of each layer. UV-visible absorption and ellipsometry revealed layer-by-layer growth of the film. The functional property film as a porous matrix was manifested in the reduction of the refractive index upon introduction of the dendrimer.     

Surface characterization of 3-glycidoxypropyltrimethoxysilane films on silicon-based substrates

Silane coupling agents are commonly used to activate surfaces for subsequent immobilization of biomolecules. The homogeneity and surface morphology of silane films is important for controlling the structural order of immobilized single-stranded DNA probes based on oligonucleotides. The surfaces of silicon wafers and glass slides with covalently attached 3-glycidoxypropyltrimethoxysilane (GOPS) have been characterized by using angularly dependent X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (ToF–SIMS), atomic force microscopy (AFM), scanning electron microscopy (SEM), and monochromatic and spectroscopic ellipsometry. XPS and ToF–SIMS data provided evidence of complete surface coverage by GOPS. Data from angularly resolved XPS and ellipsometry methods suggested that the GOPS films were of monolayer thickness. AFM and SEM data indicated the presence of films that consisted of nodules approximately 50–100 nm in diameter. Modeling suggested that the nodules may lead to a nanoscale structural morphology that might influence the hybridization kinetics and thermodynamics of immobilized oligonucleotides.     

Metastable patterning of plasma nanocomposite films by incorporating cellulose nanowhiskers

A new method is presented for developing patterned, thin nanocomposite films by introducing cellulose nanowhiskers during the pulsed plasma polymerization of maleic anhydride. Metastable film structures develop as a combination of dewetting and buckling phenomena. By controlling the maleic anhydride monomer to cellulose nanowhisker weight ratio, the whiskers can be incorporated into a homogeneously covering patterned polymer film. Excess nanowhiskers are required to prevent complete dewetting and deposit dimensionally stable films. The formation of anchoring points is assumed to stabilize the film through a "pinning" effect to the substrate. The latter control the in-plane film stresses, similar to the effects of surface inhomogeneities such as artificial scratches. The different morphologies are evaluated by optical microscopy, AFM, contact angle measurements, and ellipsometry. Further analysis by infrared spectroscopy and XPS suggests esterification between the maleic anhydride and cellulose moieties.     

Preparation and characterization of thin films of SiO(x) on gold substrates for surface plasmon resonance studies

We report here on the fabrication and characterization of stable thin films of amorphous silica (SiO(x)) deposited on glass slides coated with a 5 nm adhesion layer of titanium and 50 nm of gold, using the plasma-enhanced chemical vapor deposition (PECVD) technique. The resulting surfaces were characterized using atomic force microscopy (AFM), ellipsometry, contact angle measurements, and surface plasmon resonance (SPR). AFM analysis indicates that homogeneous films of silica with low roughness were formed on the gold surface. The deposited silica films showed excellent stability in different solvents and in piranha solution. There was no significant variation in the thickness or in the SPR signal after these harsh treatments. The Au/SiO(x) interfaces were investigated for their potential applications as new surface plasmon resonance sensor chips. Silica films with thicknesses up to 40 nm allowed visualization of the surface plasmon effect, while thicker films resulted in the loss of the SPR characteristics. SPR allowed further the determination of the silica thickness and was compared to ellipsometric results. Chemical treatment of the SiO(x) film with piranha solution led to the generation of silanol surface groups that have been coupled with a trichlorosilane.     

Sisal cellulose and its acetates: generation of films and reinforcement in a one-pot process

This study was undertaken to evaluate both the properties of cellulose acetate films as a function of their degree of substitution (DS) and the possibility of generating reinforcements during film preparation. Sisal was selected for the entire study, among other reasons, because it is a rapidly growing source of cellulose. Cellulose acetates with various DS values were prepared in a homogeneous medium (dimethylacetamide/lithium chloride as the solvent system) and characterized. In DMAc/LiCl, cellulose and cellulose acetate films (mixed or not mixed with sisal cellulose) were successfully prepared and characterized. The films with high DS values exhibited lower hygroscopicity, a distinct morphology (scanning electron microscopy images), and lower tensile strength. In some cases, the films prepared from acetates/cellulose exhibited higher tensile strength and/or storage modulus than the acetate films. This result suggested a reinforcing action of the auto-organized cellulose chains that enabled the generation of both a film and reinforcement in a one-pot process.     

Model films of cellulose ID – improved preparation method and characterization of the cellulose film

An optimization study of the preparation of spin-coated cellulose model films from the NMMO/DMSO system on silicon wafers has been made. The study shows that the cellulose concentration ID the solution determines the cellulose film thickness and that the temperature of the solution affects the surface roughness. A lower solution temperature results ID a lower surface roughness at cellulose concentrations below 0.8%. Using the described method, ID ID possible to prepare films with thicknesses of 30–90 nm with a constant surface roughness by changing the cellulose concentration, i.e. by dilution with DMSO. On these films, water has a contact angle less than 20° and about 50% of the material can, according to CP/MAS ¹³C-NMR spectroscopy on corresponding fibrous material, be considered to consist of crystalline cellulose ID type material. ID has further been shown that AFM can be used to determine the thickness of cellulose films, ID both dry and wet states. ID this method, the difference ID height between the top surface and the underlying wafer has been measured at an incision made into the cellulose film. The cellulose films have also been spin-coated with the same technique as on the silicon oxide wafer onto the crystal ID a quartz crystal microbalance (QCM). These model films were found to be suitable for swelling measurements with the QCM. The films were very stable during this type of measurement and films with different amounts of charges gave different swelling responses depending on their charges. As expected, films with a higher charge showed a higher swelling.