Dynamic mechanical thermal analysis transitions of partially and fully substituted cellulose fatty esters

The main transitions of cellulose fatty esters with different degrees of substitution (DSs) were investigated with dynamic mechanical thermal analysis. Two distinct main relaxations were observed in partially substituted cellulose esters (PSCEs). They were attributed to the glass‐transition temperature and to the chain local motion of the aliphatic substituents. The temperatures of both transitions decreased when DS or the number of carbon atoms (n) of the acyl substituent increased. Conversely, all the transitions of fully substituted cellulose esters occurred within a narrow temperature range, and they did not vary significantly with n. This phenomenon was explained by the formation of a crystalline phase of the fatty substituents. The presence of few residual OH groups in PSCEs was responsible for a large increase in the storage bending modulus, and it eliminated the effect of n on damping. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 281–288, 2003     

Photoluminescence of liquid-crystal azo derivatives in nanopores

Optics and Spectroscopy - The fluorescence of the nematic liquid crystal n-butyl-n′-methoxyazoxybenzene (BMAOB) in the form of a layer and in porous glasses with pores of different diameter...     

Transition‐metal‐catalyzed reactions of 5‐methylene‐2‐oxazolidinone and 5‐methylene‐1,3‐thiazolidine‐2‐thione with isocyanates

5‐Methylene‐2‐oxazolidinone (1) and 5‐methylene‐1,3‐thiazolidine‐2‐thione (4) react with various isocyanates to give the corresponding urethanes 3 and 5 in high yields in the presence of palladium(0) or palladium(II) catalyst under mild reaction conditions. A mechanism is proposed. Copyright © 2003 John Wiley & Sons, Ltd.     

Effect of maltodextrins on the surface activity of small-molecule surfactants

We report on the effect of commercially important polysaccharides (maltodextrins with variable dextrose equivalent (Paselli SA-2, MD-6 and MD-10) on the surface activity at the air–water interface of small-molecule surfactants (sms), possessing different hydrophobic–lipophilic balance ((SSL (Na⁺), the main component is a sodium salt of stearol–lactoyl lactic acid, and PGE (080), polyglycerol ester of C18 fatty acid), and widely used in food products. A marked change of the surface activity of sms was found in the presence of maltodextrins by tensiometry. The combined data of laser multiangle light scattering and mixing calorimetry have suggested that this result is governed by specific complex formation between maltodextrins and sms in aqueous medium. Measurements have been made of the molar mass, the second virial coefficient and the enthalpy of intermolecular interactions in aqueous solutions. The implication of a degree of polymerization of maltodextrins in this phenomenon was shown. The interrelation between the molecular parameters of the formed complexes and their surface activity at the air–water interface has been revealed and discussed.     

Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Calculation of the Radiating Characteristics of a Thermodynamically Nonuniform Gas Medium

Passive methods of remote analysis of waste gases of industrial enterprises and aircrafts engines and gases ejected in eruptions of volcanos, in fires, and in other processes disturbing the atmosphere are now of limited utility because of the lack of well-developed mathematical techniques for solving the inverse problems of gas analysis. However, the advantage of these methods is obvious, since the equipment is limited to a receiving device and the gas medium serves as a radiator. At the same time, in modern techniques, the interpretation of measurements of emissivities of gases is performed using a phenomenological approach such that experimental data on radiation characteristics of various objects are approximated by simple polynomial relations whose coefficients are determined by minimization methods. This approach does not allow one to investigate the mechanism of the processes occurring in a radiating medium and gives no way of solving the inverse problem of monitoring the composition and thermodynamic parameters of a medium which disturbs the atmosphere by thermal effects. In elaborating theoretical methods of gas analysis, the elaboration of the direct problem of calculation of radiating characteristics of gases is of importance, since it is not clear how the emissivity of a gas medium depends on its thermodynamic parameters. This paper is devoted to the above problem. Here, the error is estimated that arises in modeling a nonuniform gas medium with an actual temperature distribution, which linearly depends on coordinate, by a uniform gas layer. It is shown that the difference between the radiation intensities calculated for uniform and nonuniform media can be significant in the practically important case where the recording device is in a zone of normal temperatures. This implies that the error of reconstruction of the spectroscopic and molecular parameters of gaseous compounds from high-temperature measurements of the radiating and absorbing characteristics should take into account the thermodynamic nonuniformity of the medium.     

Research problems

This section appears from time to time. Contributions are invited, and should be submitted to R. C. Thompson, Mathematics Department, University of California, Santa Barbara, CA 93106.     

New Heat-Resistant Polyimidates Derived from Bisphenols and Mono- and Dicarboxylic Acid Imidoyl Chlorides

New polyimidates were prepared from bisphenols and mono- and dicarboxylic acid imidoyl chlorides. The structures of the polymers were determined, and their physicochemical, chemical, and thermal properties were studied. The possibility of preparing film and compression materials with good mechanical characteristics from these polymers was examined.     

Numerical study of simultaneous natural convection heat transfer from both surfaces of a uniformly heated thin plate with arbitrary inclination

 Numerical studies were conducted to investigate the natural convection heat transfer around a uniformly heated thin plate with arbitrary inclination in an infinite space. The numerical approach was based on the finite volume technique with a nonstaggered grid arrangement. For handling the pressure–velocity coupling the SIMPLE-algorithm was used. QUICK scheme and first order upwind scheme were employed for discretization of the momentum and energy convective terms respectively. Plate width and heating rate were used to vary the modified Rayleigh number over the range of 4.8×10⁶ to 1.87×10⁸. Local and average heat transfer characteristics were compared with regarding to the inclination angle. The empirical expressions for local and average Nusselt number were correlated. It has been found that for inclination angle less than 10^∘, the flow and heat transfer characteristics are complicated and the average Nusselt number can not be correlated by one equation while for inclination angle larger than 10^∘, the average Nusselt number can be correlated into an elegant correlation. Received on 18 April 2001 / Published online: 29 November 2001