Effects of aging on polyimide: A study of bulk and interface chemistry

We are investigating the bulk and interfacial chemistry of polyimide (PI) exposed to heat and relative humidity (RH) stress (85°C/85% RH) over long periods to understand the long-term reliability aspects of PI for microelectronic applications. The PI surface chemistry and the PI–Si interface chemistry was followed with electron spectroscopy for chemical analysis (ESCA). For exposure times greater than 550 h, the PI surface exhibits significant changes in emission structure and atomic concentration. The PI–Si interface indicates little change in the PI chemistry when compared to control samples. The water-contact angle at the PI surface shows no statistically significant change as a function of exposure time. Bulk and surface chemistry were followed with Fourier transform infrared spectroscopy (FTIR) in a grazing incidence reflection configuration. There were measurable differences in FTIR spectra between aged and control samples only for the case of very thin PI layers. These results suggest that for exposure times of less than 1100 h, chemical changes in PI occur primarily at the PI–air interface for samples 1 μm thick and greater. These changes represent a possible rearrangement of the imide structure and may be a form of deimidization of the polymer, but the final state is not polyamic acid. The PI surface chemistry changes observed with ESCA are reversible upon reheating to the cure temperature.     

Antibacterial modification of nylon-6 nanofibers: structure,properties and antibacterial activity.

Antibacterial nylon 6 (PA6) nanofibers have been prepared in one-step procedure using Nanospider technology. Chlorhexidine (CHX), 1-dodecyltrimethylamonium bromide (DTAB) and benzyltrimethylamonium bromide (BTAB) have been used as antibacterial agents. Samples were characterized by a series of analytical and testing methods to investigate the surface chemistry, zeta potential, structure, morphology, phase composition, mechanical properties and antibacterial activity. Experimental characterization has been combined with molecular modeling to analyze the interaction of nanofibers with modifying molecules for better understanding the effect of nanofibers modification on their properties. Antibacterial modification of PA6 led to significant changes of zeta potential (from -31 mV for PA 6 up to -49 mV for PA6/BTAB), changes in phase composition (decrease of alpha phase content and increase of gamma phase content for PA6/BTAB and PA6/CHX) and to significant increase of fiber diameter for PA6/BTAB. Antibacterial modification resulted in the straightening of nanofibers and to higher permeability of nanofiber textile for all investigated samples. Tensile tests showed the the increase of Young modulus for all the investigated samples. All the modified samples: PA6/DTAB, PA6/BTAB and PA6/CHX exhibit good antibacterial activity.     

Model-Based Analysis of Convective Grain Drying Processes

ABSTRACT

Simulation results for convective drying processes in cross-flow packed bed grain dryers are discussed in this article. A mathematical model developed in order to enable easier design of convective dryers and optimization of operating conditions for agricultural materials (wheat, corn, sunflower seed, etc.) is used in the study. On the basis of calculated values of the state variables of the gas phase and the solids, a clear image of the process itself can be obtained, as well as an overview of advantages and disadvantages of a specific design, supporting and facilitating decisions about the choice of dryer type and operating scheme. The case of double passing of drying agent, with and without additional heating, for a cross-flow continuous dryer, as well as the case of different materials processed in a series of cross-flow batch dryers, is analyzed.     

π-ELECTRON CONTENTS OF RINGS IN THE DOUBLE-HEXAGONAL-CHAIN HOMOLOGOUS SERIES (PYRENE,ANTHANTHRENE AND OTHER ACENOACENES)

Abstract

Recently three methods for calculating the π-electron content of rings of benzenoid hydrocarbons were put forward: one based on the consideration of Kekuléstructural formulas, and the other two based on an analogous treatment of the Clar aromatic sextet formulas. These three methods are applied to the homologous series consisting of two condensed acene chains (whose first members are pyrene, anthanthrene, peri-naphthacenonaphthacene, …), leading to basically identical results. In contrast to acenes (in which the partition of π-electrons into rings is uniform), in the double-hexagonal-chain species the partition of π-electrons is highly non-uniform. The electron content monotonically decreases, in opposite directions, along the two acene chains, being maximal in the least annelated rings. Some other generally valid regularities in the π-electron properties of the double–hexagonal–chain benzenoids are also pointed out.     

PARTITIONING OF π-ELECTRONS IN RINGS OF POLYCYCLIC conjugated HYDROCARBONS. PART 1: CATACONDENSED BENZENOIDS

Recently a novel view on Kekulé valence structures (or resonance structures) was reported in which their standard geometrical representation was replaced by a numerical representation obtained by assigning π-electrons associated with CC double bonds to individual benzenoid rings. In the present article, we examine in more detail the partitioning of π-electrons to benzenoid rings for cata-condensed benzenoid hydrocarbons. For special families of cata-condensed benzenoids, we offer formulas which allow one to obtain the average π-electron ring content for individual benzenoid rings of polycyclic conjugated hydrocarbons. We also show that the average π-electron ring content for individual benzenoid rings can be calculated from Pauling bond orders without a need to examine all Kekulé resonance structures of a molecule.     

Water‐soluble/dispersible carbazole‐containing random and block copolymers by nitroxide‐mediated radical polymerisation

A series of carbazole‐containing water‐dispersible poly(acrylic acid)‐b‐(9‐(4‐vinylbenzyl)‐9H‐carbazole) block copolymers (poly(AA)‐b‐poly(VBK)) and water‐soluble poly(methacrylic acid‐ran‐(9‐(4‐vinylbenzyl)‐9H‐carbazole)) (poly(MAA‐ran‐VBK)) random copolymers were synthesised in a controlled manner (i.e. low polydispersities $(\overline {M_{{\rm w}} } /\overline {M_{n} } < 1.3)$ by nitroxide‐mediated polymerisation (NMP) using an SG1‐based alkoxyamine initiator, BlocBuilder. Poly(AA)‐b‐poly(VBK) block copolymers were most easily accessed by using poly(AA) in its protected form as the macroinitiator for the 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) block. Controlled polymerisation of MAA was accomplished using an excess of 10 mol.% SG1 relative to BlocBuilder with VBK as controlling co‐monomer (initial molar feed content f_VBK,0 = 0.03–0.20) in dimethylformamide at 80°C. Poly(MAA‐ran‐VBK) copolymers with a final VBK molar composition of F_VBK < 0.30 resulted in water‐soluble copolymers. In addition, as macroinitiators, poly(MAA‐ran‐VBK)s were sufficiently pseudo‐living to reinitiate a second batch of monomer (90 mol.% methyl methacrylate with styrene) in organic solvent and by ab initio, surfactant‐free emulsion polymerisation. In both cases, low polydispersity, amphiphilic block copolymers resulted $(\overline {M_{{\rm w}} } /\overline {M_{{\rm n}} } < 1.3)$ . © 2012 Canadian Society for Chemical Engineering     

Solvothermal Conversion of Nanofiber to Nanorod‐Like Mesoporous γ‐Al2O3 Powders,and Study Their Adsorption Efficiency for Congo Red

Mesoporous γ‐Al₂O₃ powders with nanofiber and nanorod‐like structures were synthesized using boehmite sols in the presence of triblock copolymer, P123 in ethanol by solvothermal process at different temparatures (100°C–165°C) followed by calcination at 400°C–1000°C. The powders were characterized by low‐ and wide‐angle X‐ray diffraction (XRD), N₂ adsorption–desorption, and transmission electron microscopy (TEM). The adsorption efficiency of the powders with Congo red (CR) was studied by UV–vis spectroscopy. The γ‐Al₂O₃ phase became stable up to 1000°C. The nanorods obtained at 165°C had narrower pore size distribution (PSD) than nanofibers synthesized at 100°C, the former showed higher CR adsorption efficiency. The stepwise growth mechanism of nanofibers to nanorods conversion with increase in solvothermal temperatures was illustrated.     

Protection of copper surface in acidic chloride solution by non-toxic thiadiazole derivative

This paper deals with electrochemical properties of copper in the presence of the non-toxic compound 2-amino- 5-ethyl- 1,3,4-thiadiazole (AETDA) in acidic chloride solution. Electrochemical techniques: open circuit potential measurements, linear potentiodynamic measurements, cyclic voltammetry measurements and chronoamperometric measurements in addition to SEM–EDS analysis were used during the work. Results show that inhibition efficiency of 2-amino-5-ethyl-1,3,4-thiadiazole depends on inhibitor concentration and immersion time of copper electrode in inhibitor solution. Cyclic voltammetry and linear potentiodynamic measurements beside chronoamperometric measurements indicate formation of protective layer on copper surface. Moreover, results obtained by electrochemical measurements point out that the stability of formed layer depends primarily on the concentration of inhibitor and of potential values at which protective film is formed. Also, potentiodynamic measurements show that AETDA in acidic chloride solutions acts as mixed-type inhibitor. Inhibition mechanism of 2-amino-5-ethyl-1,3,4-thiadiazole includes adsorption of inhibitor on active sites on electrode surface which was confirmed by SEM–EDS analysis of the electrode surface. Adsorption of the AETDA in HCl solution obeys Langmuir adsorption isotherm.