The Impact of the Azo-Chromophore Sort on the Features of the Supramolecular Azopolyimide Films Desired to Be Used as Substrates for Flexible Electronics

High-performance supramolecular polyimide systems were synthesized via a simple and innovative approach using two types of azo-chromophores, leading to concomitant special properties: high thermostability, the ability to be processed in the form of films with high flexibility, adequate morphological features, and good structuring capacity via phase mask ultraviolet (UV) laser irradiation, induced by the presence of the azo groups (–N=N–). The dimension and the anisotropy degree of the micro/nano patterns obtained on the surface of the flexible films (determined by atomic force microscopy) depend on the azo-dye type used in the supramolecular azopolyimide synthesis, which were higher when the azo-chromophore containing a –cyano group (–C≡N) was used. The molecular dynamics method, an excellent tool for an in-depth examination of the intermolecular interactions, was used to explain the morphological aspects. Energetic, dynamic and structural parameters were calculated for the two systems containing azo-chromophores, as well as for the pristine polymer system. It was highlighted that the van der Waals forces make a major contribution to the intermolecular interactions. The results from the combination of the dynamic analysis and the concentration profile explain the better mobility of the polyimide chains with a maximum content of azo groups in the cis configuration compared to the other systems. Taking all these data into account, the surfaces of the films can be tuned as required for the proposed applications, namely as substrates for flexible electronis.     

Study on highly thermostable low-k polymer films based on fluorene-containing polyetherimides

Highly thermostable low-k polymer films with potential applications as dielectric materials in microelectronic industry were synthesized starting from 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride and various diamines. A polyetherimide/silica nanocomposite film was obtained using methyltriethoxysilane as precursor of inorganic phase. The chemical structure was confirmed by FTIR and ¹H NMR spectroscopy. Water vapor's sorption capacity, thermal stability, glass transition temperature, thermal diffusivity, specific heat, thermal conductivity, and dielectric characteristics of the films were determined. All the films exhibited excellent thermal stability, with an initial decomposition temperature in the range of 500–530°C. They showed low dielectric constant of 1.98–2.86 and low dielectric loss of 0.0037–0.011, at a frequency of 1 Hz and room temperature. The subglass γ- and β-relaxations, primary α-relaxation, and conductivity relaxation processes were discussed according to the chemical structure of the samples. Quantitative structure–property relationship (QSPR) study was conducted, and linear regression models were formulated to describe the causal relationships between different parameters and polyetherimide properties.     

Non-Lyapunov Type Stability in a Model of the Dewetted Bridgman Crystal Growth Under Zero Gravity Conditions

A numerical model has been developed based on a mass conservation level set algorithm considering a wall adhesion to predict the surface motion for a single and double dam break problems. The simulation for the single dam break shows that the wall adhesion force can be introduced through contact angle by modifying the level set function on the boundary in the level set method, and the magnitude of the contact angle has an effect on the moving location of the leading front of water–gas system. Moreover, the simulation for the double dam break presents clearly the processes of coalescence and break up of the free surface.     

Dewetted Bridgman crystal growth: practical stability over a bounded time period in a forced regime

The concept of practical stability is applied to the case of dewetted Bridgman crystal growth on Earth, in a simplified configuration. Taking into account both heat transfer and capillarity, it is formally demonstrated that the process is stable in case of convex menisci, provided that pressure fluctuations remain in a range which can be computed. The theoretical concepts are illustrated by examples involving InSb and GaSb crystal growth. It is concluded that practical stability gives valuable knowledge of the dynamics of the studied technique and could be usefully applied to other crystal-growth processes, especially those involving capillary shaping.     

Macromolecular assemblies of segmented poly(ester urethane)s and poly(ether urethane)s

Polyurethanes containing different soft and hard segments were investigated by fluorescence and scanning electron microscopy. The polarity dependence of the vibrational structure of the pyrene emission spectrum indicated the formation of aggregates at concentrations, which are significantly below the critical concentrations, which define the separation of dilute‐semidilute domains. Unlike the samples with 4,4′‐methylene diphenylene diisocyanate, the samples with 2,4‐tolylene diisocyanate in hard segments give the fluorescence spectra in which the pyrene excimer appears. The supermolecular structures associated with the form of spherulites or of spherical micelles were detected by scanning electron microscopy. The results were compared with previous reports concerning viscometric data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

An atomic force microscopy statistical analysis of laser‐induced azo‐polyimide periodic tridimensional nanogrooves

The surface morphology of azo‐polyimide films was investigated after 355nm Nd: YAG laser irradiation with two different incident fluencies. Atomic force microscopy (AFM) was employed to correlate the laser‐induced tridimensional nanogrooved surface relief with the incident fluence and the number of irradiation pulses. The height images revealed that the grooves depth increased even tens of times by increasing the incident fluence, using the same numbers of irradiation pulses. For low incident fluence, the films were uniformly patterned till 100 pulses of irradiation. Instead, when using higher fluence, after 15 pulses of irradiation the accuracy of the surface relief definition was reduced. This behavior could be explained by means of two different mechanisms, one that suppose the film photo‐fluidization due to the cis‐trans isomerization processes of the azo‐groups and the second one responsible for the directional mass displacement. The dominant surface direction and parameters like isotropy, periodicity, and period were evaluated from the polar representation for texture analysis, revealing the appearance of ordered and directionated nanostructures for most of the experimental conditions. Also, the graphical studies of the functional volume parameters have evidenced the improvement of the relief structuration during surface nanostructuration. The correlation of these statistical texture parameters with the irradiation characteristics is important in controlling the alignment of either the liquid crystals or the cells/tissues on patterned azo‐polyimide surfaces for optoelectronic devices and implantable biomaterials, respectively. Microsc. Res. Tech. 76:914–923, 2013. © 2013 Wiley Periodicals, Inc.     

Azo-polymers modified with nucleobases and their interactions with DNA molecules

The photo-fluidization process which is specific for azo-materials opens a new perspective for their use in the field of molecules nano manipulation at the surface of the azo polymer films. This is possible considering that in the case of the UV irradiation from a polarized laser source the azo material has an unidirectional flow. Here, we investigated the structuring phenomena occurring on the surface of the azo-polysiloxanes films modified with nucleobases, upon UV irradiation. Measurements of topography and adhesive forces between polymeric substrates and a hydrophilic probe have been done by atomic force microscopy (AFM). The response of the material upon irradiation has been investigated also by using UV−VIS spectroscopy. This method allowed us to draw the photo-isomerization and relaxation curves. Also, preliminary tests were conducted to determine the capacity of the film surface to immobilize DNA molecules.     

Parametric study for dewetted Bridgman method: crystal–crucible gap dependence on the Bond and Laplace numbers and on contact angle

In order to analyze the dependence of the crystal-crucible gap on the Bo and La numbers, a parametric study has been performed for two different cases: the sum of the contact angle (θ _c) and the growth angle (α _e) is smaller or larger then 180°. The limit regimes of the main parameters ( La ? - ￥,  La ? + ￥,  Bo ? + ￥,  Bo ? 0 ) \left( {La \to - \infty ,\;La \to + \infty ,\;Bo \to + \infty ,\;Bo \to 0} \right) of the problem were first studied. Then the non-dimensional Laplace equation has been solved numerically in the axi-symmetric case for various values of the parameters and the results are presented as graphical plots. It is shown that the main variations of the gap thickness are localized in the intermediary regimes. Another interesting point is that the gap thickness ([(e)\tilde] ) (\tilde{e} ) shows a maximum when the Bo and La numbers are varied. For growing crystals with a uniform radius, since, by definition, the sensitivity to small variations in the relevant parameter is minimal at the maximum, it is advisable to work at the parameter values which yield a maximum gap size.     

Interpolymer complexes between hydrophobically modified poly(methacrylic acid) and poly(N-vinylpyrrolidone)

The formation and structure of interpolymer complexes between amphiphilic multi-block copolymers—poly(dimethylsiloxane-N-vinylpyrrolidone) and poly(dimethylsiloxane-methacrylic acid)—were studied using potentiometric and conductometric titration, viscometry and fluorescence spectroscopy. The ratio of hydrophobic/hydrophilic groups in the copolymer and the molecular weight of each sequence were varied in order to establish the influence of these parameters on the interactions between the components. The complexation between pairs of block copolymers, of block copolymers and homopolymers as well as between homopolymer pairs was considered. The complexes were formed through the hydrogen bonding. They have a compact structure with a non-stoichiometric composition of pyrrolidone to methacrylic acid groups ratio around 0.6-0.7, with the exception of complexes formed between pairs of homopolymers and of copolymers with the shortest siloxane block. The difference between the new complexes and the ones formed from homopolymers, with equimolar composition, is explained by the spatial non-complementarity of the copolymers having a ‘flower-like’ structure in aqueous solutions.