Supramolecular structure formation of Langmuir-Blodgett films of comblike precursor and polyimide

The surface structure of Langmuir-Blodgett films of a comblike polyimide precursor—a rigid-chain polyamic acid alkylamine salt bearing multichains of tertiary amine—and films of the corresponding polyimide were studied by atomic force microscopy (AFM). An analysis of the images of the surface of three-layer films revealed a domain structure. It was found that the Langmuir-Blodgett film formation of the precursor occurs as a result of the layer-by-layer deposition of two-dimensional domains (composed of polyamic acid salt molecules on the water surface) onto a substrate. The formation of domains in a monolayer is associated with the chemical structure of the precursor, to be more precise, with the rigidity of the main chain and the presence of closely spaced aliphatic side chains in the polymer chain, whose total cross-section area is close to the surface area of the projection onto the plane of the repeating unit of the main chain. Polyimide films inherit the domain structure of the precursor films; the inhomogeneity of the film thickness substantially decreases, whereas the domain size and character of their distribution in the film remain unchanged.     

Formation of Langmuir-Blodgett films in solutions of comblike polymers

The structures have been analyzed of the monolayers of comblike precursor polymers of polyimides and mixed cellulose esters formed at the water/air interface and of the Langmuir-Blodgett films obtained by transfer of these condensed monolayers onto solid substrates. The important factors that ensure the structure control and supramolecular organization of these monolayers and films are established.     

Study of polyelectrolyte complexes of chitosan and sulfoethyl cellulose

The complexing of polycation chitosan and polyanion sulphoethyl cellulose during the formation of polyelectrolyte simplex membranes using the layer-by-layer deposition of a solution of one polyion on a gel-like film of another one has been studied. The structural characteristics of the multilayer composites and their components have been analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray microanalysis. A technique is proposed for studying the structure of surface layers of thin polymer films (15–20 μm) using a portable DIFREI-401 diffractometer. It is shown that the sequence of layer deposition during the formation of membrane films does not affect their structural characteristics. The interaction between positively charged chitosan groups (-NH ₃ ⁺ ) and negatively charged sulfoethyl cellulose groups (-SO ₃ ^? ) during the growth of polyelectrolyte complexes results in a packing of chitosan chains in the multilayer film.     

Study of the supramolecular structure formation of comb-like polyimide precursor Langmuir-Blodgett films

The Langmuir monolayers and Langmuir-Blodgett films of a comb-like polyimide prepolymer (the rigid-chain polyamic acid alkylamine salt bearing multichains of tertiary amine) were studied. The supramolecular structures of the monolayers and Langmuir-Blodgett films of polyamic acid salts were characterized and a way for the surpamolecular structure to form was proposed based on an analysis of the surface pressure-area isotherms of monolayers on the water surface, investigations of the conditions of monolayer deposition onto solid substrates, and studies of the structures and surface morphology of Langmuir-Blodgett films.     

X-ray diffraction study of gadolinium stearate Langmuir-Blodgett films

The comparative structural studies of gadolinium stearate Langmuir-Blodgett films prepared with the use of two different subphases (aqueous solutions of gadolinium chloride and gadolinium acetate) have been performed by the methods of X-ray diffractometry. The films were applied onto single-crystal silicon substrates coated with a native-oxide layer either with the use of buffer molecular stearic-acid layers or without such layers. It was established that the films obtained with the use of gadolinium acetate and the preliminarily formed buffer layers are, in fact, single-phase Y-type films with highly ordered molecular structure, and the thickness of the bimolecular layer d = (51.3 ± 0.5) Å.     

Atomic force microscopy study of the adsorption of protein molecules on transferred Langmuir monolayer

Ordered protein films have been obtained by the adsorption of protein molecules on a Langmuir monolayer, which had previously formed on a silicon substrate, using the Langmuir-Blodgett and molecular self-organization methods. A mixture of cholesterol with dipalmitoylphosphatidylcholine (DPPC) and a polymer—cellulose acetopivalinate—were used as immobilization materials. Protein molecules (catalase and alkaline phosphatase) immobilized on solid substrates have been investigated by atomic force micros-copy. It was shown that the developed combined technique provides a deposition of homogeneous ultrathin protein films with a high degree of filling.     

Liquid Crystal Alignment Behavior on Rubbed Films of Cellulose Acetate

The liquid crystal (LC) alignment behaviors of LC cells fabricated with cellulose acetate films were investigated. These polymer films exhibited good optical transparency in the visible light region (400–700 nm). For example, transmittance value (92%) of the cellulose acetate film onto glass substrate at 550 nm is better that (89%) of the polyimide (PI) film, the most commonly used LC alignment layers. These LC cells fabricated with the rubbed cellulose acetate films showed the homogeneous planar LC alignment with parallel direction with respect to the rubbing direction. The electro-optical characteristics of the LC cells made from the cellulose acetate films such as response time were as good as those fabricated from rubbed PI films.     

“Bands” and “Torsads” Textures in Films and Threads of Hydroxypropyl Cellulose

The present paper deals with films and threads of a mesomorphic cholesteric polymer: the hydroxypropyl cellulose. The steady flow behaviour and the shear induced textures (observed by optical microscopy under crossed polars) of films of lyotropic solutions of this polymer have been studied. A detailed analysis of the banded structures, of either the sheared solutions or the dried films obtained by solvent evaporation, is reported. We point out the existence of transverse striated patterns—“torsads”—superposed on the main banded structures, which are associated with the rewinding of the cholesteric structure following the cessation of the shear stress. The torsads, also observed in some threads, originate from the same relaxation phenomena and are discussed in the last part of the paper.     

Restoration of structure of thin multilayer films from reflectivity data by stepwise model refinement

The computational experiment on the restoration of the model parameters of the cross-section profile of the scattering density of thin multilayer films is described. It is shown that the use of the stepwise model of the structure, which is described by the thickness, density, absorption, and roughness parameters makes the problem of profile restoration multimodal and ill-conditioned. The analysis of the numerical experiments performed allowed us to propose a procedure of consecutive refinement of the initial-model parameters using the results of the local minimization of the discrepancy functional applied for the characteristic segments of the reflectivity curve. The methods proposed were used to restore the structure of a multilayer film deposited on a silicon substrate by the Langmuir-Blodgett method.     

Interaction of Se0 nanoparticles stabilized by poly(vinylpyrrolidone) with gel films of cellulose Acetobacter xylinum

The sorption and desorption of poly(vinylpyrrolidone)-Se⁰ (PVP-Se⁰) nanoparticles on gel films of cellulose Acetobacter xylinum (CAX) are investigated. It is revealed that the hydrodynamic radius R _h of PVP-Se⁰ nanoparticles decreases from 57 nm in the initial solution (without CAX gel films) to 25 nm after the sorption of nanostructures on gel films and then increases to approximately 100 nm after the desorption of nanoparticles with water from dry samples of the CAX gel film-PVP-Se⁰ nanocomposite. It is found that selenium atoms do not penetrate into crystallites of the cellulose nanofibrils and replace water molecules sorbed by the primary hydroxyl groups of their walls. Poly(vinylpyrrolidone)-Se⁰ nanoclusters differ in the number and size upon their sorption inside the cellulose gel film and on the film surface.     

Determination of the size and phase composition of silver nanoparticles in a gel film of bacterial cellulose by small-angle X-ray scattering,electron diffraction,and electron microscopy

The nanoscale structural features in a composite (gel film of Acetobacter Xylinum cellulose with adsorbed silver nanoparticles, stabilized by N-polyvinylpyrrolidone) have been investigated by small-angle X-ray scattering. The size distributions of inhomogeneities in the porous structure of the cellulose matrix and the size distributions of silver nanoparticles in the composite have been determined. It is shown that the sizes of synthesized nanoparticles correlate with the sizes of inhomogeneities in the gel film. Particles of larger size (with radii up to 100 nm) have also been found. Electron microscopy of thin cross sections of a dried composite layer showed that large particles are located on the cellulose layer surface. Electron diffraction revealed a crystal structure of silver nanoparticles in the composite.     

Optical studies of aromatic polyazomethine thin films

Optical transmission and fundamental reflectivity spectra of aromatic polyazomethine thin films, obtained by vacuum evaporation via the polycondensation process have been investigated in the wide spectral range 0.49–6.2 eV. As initial monomers, terephaldehyde (TPA) and one of four different amines, i.e. paraphenylene-diamine (PPDA), 7,2-diamino-fluorene, 1,1′-biphenyl-3,3′,4,4′-tetramine and 3-amino-4-(1-naphthyldiazenyl)phenylamine (fat brown RR) have been used, respectively. Amorphous character of these films was confirmed by the results of X-ray diffraction and AFM investigations. Absorption coefficient of the films has been obtained and the edge of absorption seems to be similar to the absorption edge typical for amorphous semiconductors, what allowed to obtain the Urbach energy and E_T parameter. The energy gaps of the films, following the Tauc relation, are found to change from 2.05 to 2.4 eV, depending on the length of conjugated part of the polymer chain. Absorption bands above the absorption edge, observed for different polyazomethine films are connected with their chemical structure and possible electronic transitions.     

Controlling the absorption and emission properties of polyparaphenylenevinylene films

In this work we used the conversion process of a precursor polymer into polyparaphenylenevinylene (PPV) at low temperatures in order to control the effective conjugation degree of spin-casted PPV films. The absorption and emission spectra of the films were studied by following a partial substitution of chloride counterions from poly(xylylidene tetrahydrothiophenium chloride) (PTHT), used as a precursor, by sodium acid dodecylbenzenesulfonate (DBS), added as a surfactant salt. Upon controlling the DBS amount and conversion temperature (T_c) of PTHT/DBS to PPV films, the band gap of PPV changed from 409 to 506 nm, and 505 to 532 nm, values obtained from absorbance and emission measurements, respectively. Based on these experimental data, we proposed a physical model which represents the chemical structure of PPV as a distribution of conjugated chain segments (like oligomers) alternated by non-conjugated segments (structural defects and/or from the precursor polymer).     

Structure of cellulose <Emphasis Type="Italic">Acetobacter xylinum</Emphasis>

The data are presented on optimization of cellulose synthesis by Acetobacter xylinum (strain VKM V-880) and the structural characteristics of A. xylinum cellulose gel film synthesized during static cultivation. The structural changes caused by the removal of water from gel films are established and the structural organization of macromolecular chains in cellulose A. xylinum is studied.     

Influence of water on localized and delocalized molecular mobility of cellulose

The influence of hydration on cellulose molecular mobility is investigated by two dielectric methods at different molecular scale. The mobility of side groups, assigned to γ mode, for dried cellulose increases. The water molecules have an anti-plasticizer effect on γ mode due to the water–polymer hydrogen bonding. For the β relaxation mode, only observed by the Thermo Stimulated Current technique, the hydration plays a role of plasticizer. The α relaxation mode assigned to the delocalized cooperative mobility of long chain segments of cellulose is plasticized by water. The study of activated parameters deduced from fractional polarization procedure, shows an increase of the activation enthalpy range with dehydration. It permits to conclude that reduction of hydrogen bonds density leading to a more extended cooperative mobility.     

On two-dimensional ferroelectricity in layered polymer films on substrates

A simple model for describing structural phase transitions in thin ferroelectric copolymer films on solid substrates obtained by the Langmuir-Blodgett method has been suggested. It is shown that the polymer-substrate interaction and surface tension considerably influence these transitions and, in particular, can induce additional low-temperature first-and second-order phase transitions depending on the material parameters and the film thickness. The main dimensionless parameter and its critical value, which control the formation of the additional order in very thin films, are determined.     

Growth from Solution,Structure, and Optical Properties of Single-Crystal <Emphasis Type="Italic">para</Emphasis>-Quaterphenyl Films

Samples of single-crystal para-quaterphenyl films up to 8 mm long and 50 μm thick have been obtained for the first time by the solvent?antisolvent growth method. The films have been grown both on the liquid–air interface and in the solution bulk. The morphology, surface quality, and thickness of crystal films have been investigated by the optical, laser confocal, and atomic force microscopies. The structure of the para-quaterphenyl single crystal at room temperature has been refined by X-ray diffraction analysis. The formation and growth mechanisms of crystal films on the liquid–air interface have been discussed. The opticalabsorption and photoluminescence spectra of the solutions and crystal samples have been investigated.     

X-Ray diffraction study of the evolution of phase and structural state and macroscopic stress during annealing of soft magnetic Fe95 − x Zr5N x films prepared by ion-plasma deposition

The evolution of the phase composition, nanostructure parameters, and macroscopic stress in soft magnetic Fe_{95 ? x} Zr₅N _x films (prepared by ion-plasma deposition onto quartz substrates) during their annealing has been investigated by X-ray diffraction. During deposition, depending on the N content, either a mixed structure composed of an X-ray amorphous phase enriched in Zr and N and a crystalline phase (α-Fe(N) solid solution) or an X-ray amorphous phase enriched in Fe, Zr, and N is formed in the films. During annealing, depending on the temperature and nitrogen content, different combinations of crystalline phases (α-Fe(N) and Zr(N) solid solutions, α-Fe, Fe₄N, Fe₂N, ZrO₂) are formed in the films. The large compressive stress formed in the films during deposition changes to a lower tensile stress during annealing.     

Growth and structure of barium sodium orthoborate NaBaBO3 crystals

Crystals of NaBaBO₃ were grown by spontaneous crystallization on a platinum loop from the BaO-B₂O₃-Na₂O system using the flux technique. The crystals have a highly disordered block structure. X-ray diffraction study λMoKα, 518 independent reflections, R = 0.0272) demonstrated that the structure of these crystals is identical with that established previously by other researchers for a sample prepared by cooling a stoichiometric melt.     

Structures of vapour-deposited amorphous films of arsenic chalcogenides

The structures of vapour-deposited amorphous films of composition As_xSe_1?x′, with x between 0 and 1, have been investigated by X-ray diffraction. In all cases the structure of the freshly deposited film differs very considerably from that of the corresponding bulk glass. For the elemental amorphous films the structure is highly disordered and contains voids which for Se cannot be annealed out below the crystallization temperature of 70°C or, for As, below the temperature ($\text{?130°}\text{C}$) where the As film re-evaporated. Annealing of the arsenic selenide films at temperatures below T_g causes the structures to relax towards those of the bulk, with a distribution of activation energies around 25 kJ mol^?1. The composition of the vapour has been examined by mass spectroscopy and it is concluded that even if some molecular identity is retained on condensation there must be considerable cross-linking to give the observed structural behaviour.