A generalized equation for the prediction of melting temperatures of homopolymers and copolymers

A generalized equation was derived to calculate the melting temperatures of homopolymers and copolymers. The Gibbs‐Thomson equation for homopolymers and a modified application to copolymers were derived using the proposed equation. The melting temperature T_m⁰ in the Flory equation corresponds to the melting temperature T_m^C,∞ of copolymer crystals with stems of infinite length. Also, T_m^C,n*, the melting temperature for copolymer crystals with stems containing the maximum possible number of structural units, n*, should be used instead of T_m⁰ as the basis of supercooling in crystallization. The proposed equation shows good agreement with experimental data for α‐alkene‐ethylene homogeneous copolymers.     

A New Variable Diffusion Drying Model for the Second Falling Rate Period of Paddy Dried in a Rapid Bin Dryer

The objectives of this article is to propose a new drying model for the second falling rate period known as the variable diffusion controlled period that follows after the first falling rate period and to propose a new method to determine the second critical moisture content that separates these two periods. Experimental work on paddy drying at minimum fluidization velocity was carried out in a rapid bin dryer. The effects of operating temperatures (60-120°C) and bed depths (2-6 cm) on the paddy drying characteristics were investigated. It was found that the normalized drying rate of paddy was proportional to the normalized moisture content in the first falling rate period but in the second falling rate period, the normalized drying rate of the material varies exponentially with the normalized moisture content. The different relationship between the normalized drying rate and the normalized moisture content in the first and second falling rate periods indicate that two different mechanism of moisture transport are at work. The new exponential model of the second falling rate period and the linear model of the first falling rate period were found to fit the experimental data very well. Derivation from variable diffusion equation shows that the linear model is the result of constant diffusion coefficient whereas the new exponential model is the result of linear diffusion coefficient. This also implies that the first falling rate period is a constant diffusion controlled period and the second falling rate period is a variable diffusion controlled period. In addition, drying kinetics data of a drying process that fits the exponential model over a very slow drying period will show that the drying process is under the effect of a linear diffusion coefficient. It was also found that the proposed new method to determine the second critical moisture content that distinguishes between the first and second falling rate periods by using a sudden change in the value of the drying rate gradient to a much lower value at that point is more rigorous and yet simpler than the method of determining the specific location of the receding drying boundary since it is based on the behavior of the actual drying kinetic data.     

Impacts of varnishes and impregnation chemicals on combustion properties of oak (Quercus petreae lipsky)

This study was performed to determine the effects of varnishing after impregnation with boron compounds on combustion properties of oak. For this aim, the test samples prepared from oak (Quercus petreae Liebl.) wood were impregnated according to ASTM D 1413‐99 with boric acid (Ba) and borax (Bx) by vacuum technique. After impregnation, surfaces were coated by cellulosic (Cv), synthetic (Sn), polyurethane (Pu), waterborne (Wb), acrylic (Ac), and acid hardening (Ah) varnishes in accordance to ASTM D 3023. Combustion properties of samples after varnishing process were determined, according to ASTM E 160‐50. According to material and process types, combustion temperature was the highest in Bx and Cv, the lowest in Ba and Ac. An important difference was not observed between without flame source combustion (WFSC) and flame source combustion (FSC). According to combustion type, impregnation material and varnish type, combustion temperature was the highest value in WFSC + Bx + acid hardening varnish combination and the lowest in WFSC + Ba + acrylic varnish combination. As a result, the tested varnishes showed an increasing impact but boron compounds showed a decreasing impact on combustion properties of oak. In consequence, for usage areas having a high risk of fire, impregnation of wood material with boron compounds before varnishing will decrease combustion temperature and provide security. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Varnish layer hardness of oriental beech (fagus orientalist L.) wood as affected by impregnation and bleaching

The impacts of impregnation and bleaching on the varnish layer hardness of Oriental beech (Fagus orientalist L.) wood were investigated. A number of bleaching combinations {[NaOH−H₂O₂], [NaOH−Ca(OH)₂−H₂O₂], [NaOH−MgSO₄−H₂O₂] [NaHSO₃−H₂C₂O₄], [NaSiO₃−H₂O₂], [KMnO₄+NaHSO₃+H₂O₃]} were applied at 18% concentration for bleaching to both impregnated and unimpregnated specimens of Oriental beech wood. Subsequently, water-based (WB) varnish was coated over the samples and the varnish layer hardness values were determined in accordance with ASTM D 4366-95. All of the chemicals used for bleaching reduced the surface hardness. However, after varnish coating, the hardness of most samples was similar to that of the varnish-coated natural (control) samples.     

Comparison between some empirical equations of state for polymers

Some commonly used empirical equations of state for polymers are considered: the Spencer-Gilmore equation with two and three adjustable parameters, the Whitaker-Griskey equation, and the Rehage-Breuer equation. Also, a new equation is proposed: the Inverse Volume equation. These equations are evaluated with regard to fitting experimental P-V-T data and agreement with experimental data on isothermal compressibility and thermal expansion coefficient. The adjustable parameters for each equation are determined with the help of Rosenbrock's optimum-seeking technique. Analysis of the residuals on specific volume for a variety of materials suggests that the Spencer-Gilmore equation with three adjustable parameters, the Rehage-Breuer and the Inverse Volume equations yield the smallest and most random residuals and thus the least systematic error. The same three equations mentioned above yield results in good agreement with experimental isothermal compressibility data. However, among all the equations considered in this study, the Inverse Volume equation yields the best agreement with experimental thermal expansion coefficient data. Furthermore, it is the only equation to correctly predict the rise in thermal expansion coefficient with increasing temperature.     

Distributions of Crystal Size from DSC Melting Traces for Polyethylenes

Melting curves, obtained by differential scanning calorimetry, are used to estimate crystal size distributions. The proposed theoretical analysis is applied to different types of polyethylene, including high‐density polyethylene (HDPE), metallocene catalyzed linear low‐density polyethylenes (m‐LLDPE), blends of m‐LLDPEs, and Ziegler‐Natta catalyzed LLDPEs (ZN‐LLDPE). Theoretical predictions are in agreement with experimental results. A generalized melting temperature equation successfully predicts the melting temperatures of all the LLDPEs, although it was initially proposed for homogeneous copolymers with excluded comonomers. A new definition of the heat of fusion for pure crystals is proposed. This heat of fusion can be calculated from the average crystal size or the crystal size number distribution.     

Fuzzy functions based ARX model and new fuzzy basis function models for nonlinear system identification

In this study, auto regressive with exogenous input (ARX) modeling is improved with fuzzy functions concept (FF-ARX). Fuzzy function with least squares estimation (FF-LSE) method has been recently developed and widely used with a small improvement with respect to least squares estimation method (LSE). FF-LSE is structured with only inputs and their membership values. This proposed model aims to increase the capability of the FF-LSE by widening the regression matrix with lagged input–output values. In addition, by using same idea, we proposed also two new fuzzy basis function models. In the first, basis of the fuzzy system and lagged input–output values are structured together in the regression matrix and named as “L-FBF”. Secondly, instead of using basis function, the membership values of the lagged input–output values are used in the regression matrix by using Gaussian membership functions, called “M-FBF”. Therefore, the power of the fuzzy basis function is also enhanced. For the corresponding models, antecedent part parameters for the input vectors are determined with fuzzy c-means (FCM) clustering algorithm. The consequent parameters of the all models are estimated with the LSE. The proposed models are utilized and compared for the identification of nonlinear benchmark problems.     

Fabrication of ultraviolet photoconductive sensor using a novel aluminium-doped zinc oxide nanorod-nanoflake network thin film prepared via ultrasonic-assisted sol-gel and immersion methods

Unique and novel thin films with aluminium (Al)-doped zinc oxide (ZnO) nanostructures consisting of nanorod-nanoflake networks were prepared for metal-semiconductor-metal (MSM)-type ultraviolet (UV) photoconductive sensor applications. These nanostructures were grown on a glass substrate coated with a seed layer using a combination of ultrasonic-assisted sol-gel and immersion methods. The synthesised ZnO nanorods had diameters varying from 10 to 40 nm. Very thin nanoflake structures were grown vertically and horizontally on top of the nanorod array. The thin film had good ZnO crystallinity with a root mean square roughness of approximately 13.59 nm. The photocurrent properties for the Al-doped ZnO nanorod-nanoflake thin films were more than 1.5 times greater than those of the seed layer when the sensor was illuminated with 365 nm UV light at a density of 5 mA/cm². The responsivity of the device was found to be dependent on the bias voltage. We found that similar photocurrent curves were produced over eight cycles, which indicated that the UV sensing capability of the fabricated sensor was highly reproducible. Our results provide a new approach for utilising the novel structure of Al-doped ZnO thin films with a nanorod-nanoflake network for UV sensor applications. To the best of our knowledge, UV photoconductive sensors using Al-doped ZnO thin films with a nanorod-nanoflake network have not yet been reported.