Synthesis of amphiphilic (meth)acrylates with oligo(ethylene glycol) and (or) oligo(propylene glycol) blocks by the esterification of (meth)acrylic acid

Thermoresponsive PEG-based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)- or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate- and methoxy oligo(propylene glycol)-block-oligo(ethylene glycol) (meth)acrylate-based macromonomers with high yields (80%–98.7%) by the acid-catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p-Toluene sulphonic acid (pTSA), alkyl(C₁₂–C₁₄)benzene sulfonic acid (ABSA) and H₂SO₄ were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%.     

Monitoring the curing processes of epoxy oligomers with partially substituted polyethoxymetallosiloxanes by IR spectroscopy and thermomechanical analysis

In this work, the curing of «ED-20» epoxy resin with partially siloxy-substituted aluminum, iron, and zirconium siloxanes that we obtained previously was studied. The initial content of a metallosiloxane in the compositions was 5–50 wt% with respect to the resin. In all the cases, thermal curing was used to obtain a series of samples in the form of solid homogeneous materials. The fact of the epoxy ring opening in the resin was confirmed by IR spectroscopy. The catalytic properties of the metal atom in a metallosiloxane were found to affect the curing process. The samples demonstrate rather a high resistance to thermooxidative destruction, and in most cases, their glass transition temperatures are lower than those obtained upon standard curing of «ED-20» resin with triethylenetetramine. Partially siloxy-substituted metalloalkoxysiloxanes can be efficient agents for curing and formation of a hybrid material based on epoxy resins.     

Biobased flexible polyurethane foams manufactured from lactide-based polyester-ether polyols for automotive applications

In this study, biobased polyester-ether polyols derived from meso-lactide and dimer acids were evaluated for flexible polyurethane foams (PUF) applications. Initially, the catalyst concentration was optimized for the biobased PUF containing 30% of biobased polyol (70% petroleum-based polyol). Then, the same formulation was used for biobased PUF synthesis containing 10%–40% of biobased polyols. The performance of biobased PUF was compared with the performance of the control foam made with 100% petroleum-based polyol. The characteristic times (cream, top of the cup, string gel, rise, tack-free) of biobased PUF were determined. The biobased PUF were evaluated for the mechanical (tensile and compressive) and morphological properties. As the wet compression set is important for automotive applications, it was measured for all biobased PUF. The thermal degradation behavior of biobased PUF was also evaluated and compared with the control foam. The effect of different hydroxyl and acid values of polyols on the mechanical properties of biobased PUF is also discussed. The miscibility of all components of PUF formulations is crucial in order to produce a foam with uniform properties. Thus, the miscibility of biobased polyols with commercial petroleum-based polyol was studied.     

Self-Diffusion of Iron in Molten Fe-C Alloys

Self-diffusion coefficients of iron in molten Fe-C alloys have been measured by using the capillary method. In addition, the samples have been autoradiographed and sectioned to insure that no significant convection has occurred during the diffusion. The results can be represented by the equation D = 4.3×10^?3 exp (—12.200/RT) for carbon = 4.6 pct and T = 1513° to 1633°K; and D = 1.0×10^?2 exp (—15,700/RT) for carbon = 2.5 pct and T = 1613° to 1673°K. The D values are higher and the heat of activation for diffusion lower in alloys containing more carbon. Calculation based on the Einstein-Stokes equation indicates that the diffusing species is iron ion.     

Effect of ZrO<Subscript>2</Subscript> coating on<Emphasis Type="Italic">in vitro</Emphasis> formation of calcium phosphate

We prepared zirconia thin films on (100) Si wafer by using a chemical solution deposition with a zirconium naphthenate as a starting material. The films were pyrolyzed at 500°C for 10 min and finally annealed for 30 min in air at 500°C. Amorphous films after annealing had no distinct structure and were uniform along the cross section line.In vitro formation of the calcium phosphate was evaluated by the field emission-scanning electron microscope, energy dispersive X-ray spectrometer and Fourier transform infrared spectroscopy.     

Processing,deformation, and failure in superplastic aluminum alloys: Applications of orientation-imaging microscopy

The importance of grain size refinement in enabling superplasticity is reviewed, and the current understanding of grain boundary characteristics is summarized. The application of orientation-imaging microscopy (OIM) methods to the processing response and the deformation and failure modes in superplastic aluminum alloys are illustrated through microtexture analysis and determination of grain boundary characteristics in selected commercial materials. Continuous and discontinuous recrystallization reactions exhibit distinct microtextures and grain boundary characteristics. The application of OIM and microtexture analysis to the evaluation of both deformation and failure mechanisms during superplastic forming is illustrated. This paper was presented at the International Symposium on Superplasticity and Superplastic Forming, sponsored by the Manufacturing Critical Sector at the ASM International AeroMat 2004 Conference and Exposition, June 8–9, 2004, in Seattle, WA. The symposium was organized by Daniel G. Sanders, The Boeing Company.     

Effects of different metallurgical processing on microstructures and mechanical properties of inconel alloy 783

Different metallurgical processing, including the standard heat treatment, heat treatment without β aging, addition of high amount of Cr, and long-term isothermal exposure, was conducted on superalloy Inconel 783. For these processed materials, the tensile property and hardness at room temperature and stress relaxation behavior at 650 °C were examined. The testing results showed that isothermal exposure and heat treatment without β aging slightly enhanced the yield strength of alloy 783 at room temperature as well as all metallurgical processing in this study produced an identical stress relaxation behavior at 650 °C. The microstructure variation with different processing was analyzed using optical microscope, scanning electron microscopy (SEM), and transmission electron microscopy (TEM).