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.     

Synthesis and characterization of hydroxyl terminated poly(butadiene)-g-poly(glycidyl azide) copolymer as a new energetic propellant binder

Summary Poly(glycidyl azide), PGA, was grafted onto Hydroxyl Terminated Poly(butadiene), HTPB, via free radical mechanism. PGA-macro azoinitator and HTPB polymer mixture was casted from solution and the polymer film was kept at 90°C for 4 hours. The grafted polymer was isolated from the product by fractional precipitation and characterized by NMR and FT-IR spectroscopy. Graft copolymer structure was also confirmed that volume ratio of nonsolvent to the solution of the graft copolymer was between those of corresponding homopolymers. TGA traces of the block polymers were containing two different maxima at 253°C (for PGA units) and 469°C (for HTPB units). Because of the incompatibility of the blocks, DSC curve showed two T_g's which belong to the related segments.     

Surface modification of polyester and polyamide fabrics by low frequency plasma polymerization of acrylic acid

In this study, the surface characteristics of polyester and polyamide fabrics were changed by plasma polymerization technique utilizing acrylic acid as precursor. This monomer was used to produce hydrophilic materials with extended absorbency. The hydrophilicity, total wrinkle recovery angle (WRA°) and breaking strength of the fabrics were determined prior and after plasma polymerization treatment. The modification of surfaces was carried out at low pressure (<100 Pa) and low temperature (<50°C) plasma conditions. The effects of exposure time and discharge power parameters were optimized by comparing properties of the fabrics before and after plasma polymerization treatments. It was shown that two sides of polyester fabric samples were treated equally and homogeneously in plasma reactor. For polyester fabrics, the minimum wetting time, 0.5 s, was observed at two plasma processing parameters of 10 W–45 min and 10 W–20 min, where untreated fabric has a wetting time of 6 s. For polyester fabrics, the maximum value was obtained at 60 W–5 min with the wrinkle recovery angle of 306° where the untreated fabric has 290°. The optimum plasma conditions for polyamide fabrics were determined as 30 W–45 min where 2 s wetting time was observed. Wrinkle recovery angle of untreated polyamide fabric was 264°. In this study, after plasma polymerization of acrylic acid, wrinkle recovery angle values were increased by 13%. No significant change was observed in breaking strength of both fabrics after plasma treatment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2318–2322, 2007     

Treatment of phenol formaldehyde production wastewater by electrooxidation-electrofenton successive processes

ABSTRACT

Treatments of phenol formaldehyde producing wastewater (PFPW) by electrooxidation (EO) and electro-Fenton (EF) successive processes were carried out in a batch electrolytic reactor using graphite (Gr) and stainless steel (Ss) electrodes. After the completion of the EO process, the wastewater was further treated with EF process. The influence of operating variables such as current density, operating time, initial pH_i and H₂O₂ concentration was evaluated for removals of phenol, TOC and COD in PFPW. Gr/Gr, Gr/Ss or Ss/Ss and Ss/Gr electrode pair were used as anode and cathode. The best removal efficiency in the EO process was obtained with Gr/Gr (93%) as compared to Gr/Ss (82%), Ss/Ss (63%) and Ss/Gr (55%). The removal efficiencies for the EO process using Gr-Gr electrode pair were obtained as 93% for phenol, 61% for COD and 44% for TOC at initial pH_i 7,5 g/L of NaCl, 50 mA/cm² and 5 h. In the EF process, the removal efficiencies at pH_i 3,5 mA/cm² and 30 mM H₂O₂ and 45 min were 100% for phenol, 76% for COD and 59% for TOC. This study provided that the successive processes are an effective method for the removal of phenolic compounds from the wastewater.     

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.     

Mullite for Structural, Electronic, and Optical Applications

Mullite (3Al₂O₃·2SiO₂) is becoming increasingly important in electronic, optical, and high-temperature structural applications. This paper reviews the current state of mullite-related research at a fundamental level, within the framework of phase equilibria, crystal structure, synthesis, processing, and properties. Phase equilibria are discussed in terms of the problems associated with the nucleation kinetics of mullite and the large variations observed in the solid-solution range. The incongruent melting behavior of mullite is now widely accepted. Large variations in the solid solubility from 58 to 76 mol% alumina are related to the ordering/disordering of oxygen vacancies and are strongly coupled with the method of synthesis used to form mullite. Similarly, reaction sequences which lead to the formation of mullite upon heating depend on the spatial scale at which the components are mixed. Mixing at the atomic level is useful for low-temperature (<1000°C) synthesis of mullite but not for low-temperature sintering. In contrast, precursors that are segregated are better suited for low-temperature (1250° to 1500°C) densification through viscous deformation. Flexural strength and creep resistance at elevated temperatures are significantly affected by the presence of glassy boundary inclusions; in the absence of glassy inclusions, polycrystalline mullite retains >90% of its room-temperature strength to 1500°C and displays very high creep resistance. Because of its low dielectric constant, mullite has now emerged as a substrate material in high-performance packaging applications. Interest in optical applications mainly centers on its applicability as a window material within the mid-infrared range.     

Fine grinding of thermoplastics by high speed friction grinding assisted by guar gum

High speed friction grinding has been used to grind plant and food substances in water but never been explored for grinding of thermoplastics like polylactic acid (PLA), low and high density polyethylene and polypropylene. Such grinding was investigated in this work and was made possible by using 0.5% guar gum solution instead of just water because increasing the viscosity of water reduced their settling and the speed of passing through the grinder. Tensile, flexural, and impact strengths of the plastics were studied and higher grinding efficiency of PLA could be explained by its low elongation-at-break compared to low density polyethylene, high density polyethylene, and polypropylene. The microplastics (2000–45 μm) were studied for mass and particle size distributions and by scanning electron microscopy, ¹³C CP/MAS NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. In addition, viscosity of guar gum and contact angles was measured. This new technology can produce finely ground microplastics (710–45 μm) for a variety of applications.     

Graphite intercalated polymer coatings on stainless steel

The use of graphite modified polymer films has been investigated, on stainless steel. Polythiophene and polypyrrole films have been synthesized electrochemically on stainless steel, and then very thin graphite layers were realized on polymer films. Since the graphite layer is not applicable as a top coat, polymeric top films were also electrosynthesized on graphite layers. Following this procedure, polypyrrole-graphite-polypyrrole and polythiophene-graphite-polythiophene coatings have been obtained on stainless steel. The corrosion behaviours of coated samples have been investigated in 0.1 M H₂SO₄ solution, by means of electrochemical impedance spectroscopy (EIS) and anodic polarization curves. The intercalation of graphite layer altered the performance and properties of coatings significantly. Especially, polypyrrole coating system was found to exhibit almost an excellent coating behaviour that hindered the attack of corrosive environment within 96 h exposure time. The EIS results of polypyrrole coating system were indicating to almost a perfect capacitive behaviour that the response was reflecting capacitive behaviour in a wide frequency region. This property was also examined with successive cyclic voltammograms in a potential range between 0.10 and 0.40 V (vs. Ag/AgCl). The charge densities involved in oxidation and reduction regions were determined for successive cycles and it was shown that coated sample was able to exhibit charge-discharge (i.e. oxidation and reduction) behaviour successfully, without any degradation.     

High-capacity quantum key distribution using Chebyshev-map values corresponding to Lucas numbers coding

We propose an approach that achieves high-capacity quantum key distribution using Chebyshev-map values corresponding to Lucas numbers coding. In particular, we encode a key with the Chebyshev-map values corresponding to Lucas numbers and then use k-Chebyshev maps to achieve consecutive and flexible key expansion and apply the pre-shared classical information between Alice and Bob and fountain codes for privacy amplification to solve the security of the exchange of classical information via the classical channel. Consequently, our high-capacity protocol does not have the limitations imposed by orbital angular momentum and down-conversion bandwidths, and it meets the requirements for longer distances and lower error rates simultaneously.