Epoxy fatty acid ester plasticizers. Preparation and properties

Summary The preparation of epoxy fatty acid ester plasticizers has been reviewed. These plasticizers can be prepared by epoxidation reactions, utilizing a preformed peracid or anin-situ technique. A newin-situ epoxidation process, utilizing hydrogen peroxide and acetic acid in the presence of strong acid catalyst, has been described. Excellent conversions to epoxide have been achieved with a series of monounsaturated and polyunsaturated esters. Epoxy fatty acid esters are excellent plasticizers for vinyl resins. Their performance in a series of additional epoxy plasticizers of vegetable and marine origin is described. Novel epoxy plasticizers based upon mixed acetylated mono- and di-glyceride have been prepared and are found to have excellent plasticizer performance. Presented at the 28th fall meeting, American Oil Chemists’ Society, October 1954, Minneapolis, Minn.     

Mechanical Behavior of Several Hybrid Ceramic-Matrix-Composite Laminates

Several different hybrid laminated composites comprised of alternating layers of dense ceramic sheets (either SiC or Si₃N₄) and fiber-reinforced ceramic-matrix-composite (CMC) layers (Nicalon fibers with either glass or glass-ceramic matrices) have been fabricated and characterized. The effects of the reinforcement architecture (unidirectional vs cross-ply) and the relative volume fractions of the phases on the tensile and flexural properties have been examined. Comparisons have been made with the properties of the constituent layers. Rudimentary models have been developed to describe the onset of cracking and for the minimum volume fraction of CMC required to develop multiple cracks and thus obtain a high failure strain.     

Preparation and characterization of a number of amine salts of long-chain fatty acids

Summary Eighty-eight amine salts of long-chain fatty acids have been prepared, purified by solvent crystallization, and characterized. Forty-five of these were salts of palmitic acid. The rest included salts of capric, lauric, myristic, stearic, oleic, elaidic, and 12-hydroxystearic acids. A variety of aliphatic, aromatic, and heterocyclic amines, including primary, secondary, and tertiary amines, were investigated. The majority of these gave 1∶1 acid-amine compounds on solvent recrystallization of an equimolar mixture of acid and amine. Some of the amines gave no crystallizable salt, and with others the pure salt could not be obtained by this procedure. Under the same conditions the symmetrical alkyl, substituted alkyl, and aralkyl secondary amines investigated gave crystallizable compounds containg two molecules of fatty acid to one of amine. Molecular compounds of 2-aminopyridine with four molecules of saturated fatty acid were formed by recrystallization starting with a 1 to 4 amine-acid mixture. Surface-tension measurements were made for aqueous solutions of a few of the amine salts. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Fatty acid morpholides as plasticizers for vinyl chloride resins. III. Ternary compatibility-composition diagrams for the oleic-linoleic-stearic and oleic-linoleic-palmitic systems

A systematic investigation has been made of the effect of fatty acid composition on the compatibility of the corresponding mixed morpholides as plasticizers for vinyl chloride-vinyl acetate copolymer resins. Plasticizer evaluation data were obtained for the morpholides of lauric, palmitic, elaidic, and epoxyoleic acids and compared with the literature values for other fatty acid morpholides and morpholide mixtures. Ternary compatibility-composition diagrams have been constructured for the oleic-linoleic-stearic and the oleic-linoleic-palmitic morpholide systems. These diagrams make it possible to predict what adjustment, if any, must be made in the composition of any mixture of these fatty acids so that the corresponding morpholide mixture will be compatible. The diagrams will be useful in selecting the most appropriate and economical fatty acid sources from which to make compatible morpholide mixtures. Presented at the 52nd Annual Meeting, American Oil Chemists’ Society, St. Louis, Mo., May 1–3, 1961. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Carbon fiber structure and stability studies

A study has been made of the thermal-oxidative stability of several commercially available carbon fibers. Significant differences in the weight loss behavior were observed in air aging studies run on the bare fibers at 600°F (589 K). The stability of high temperature laminates, such as those based on NR-150 polyimide precursor solutions, was found to be directly affected by the stability of the reinforcing carbon fibers. In studies carried out to determine the reasons for carbon fiber instability, residual sodium sulfate was found to be the principle destabilizing factor. A mechanism whereby the sodium sulfate promotes the oxidation of carbon in the presence of air is proposed.     

Studies of microhardness and mar resistance using a scanning probe microscope

Scanning probe microscopy (SPM) is in a period of rapid development. It shows great promise for characterizing coating surfaces. This paper describes modification of an SPM so that it can be used to mar the surfaces of coatings under controlled conditions and to characterize the mars. Mar resistance of coatings is analyzed in terms of a ‘three response, two mechanism model.' The three responses (fracture, elastic, and plastic) can be measured quantitatively using the SPM. Of the three responses, only two (fracture and plastic deformation) are marring mechanisms – elastic deformations recover instantaneously. In some cases mars resulting from plastic deformation may recover slowly with time or with immersion in water; this phenomenon is attributed to viscoelastic creep. Microhardness is also measured with the modified SPM. Some thermoset coatings appear to be substantially harder near their surfaces than in the mass of material, and such materials may respond quite differently to stress applied at different levels near the surface. This finding has important implications for all coating properties that are strongly influenced by the surface. A quantity called ‘micro mar resistance' is defined. It may be useful for comparing different coatings under specified conditions of marring. However, there can be no single quantity that expresses ‘mar resistance' of a coating under all conditions.     

Modelling formation and growth of H2SO4-H2O aerosols: Uncertainty analysis and experimental evaluation

An aerosol dynamics model, AERO2, is presented, which describes the formation of H₂SO₄-H₂O aerosol in a smog chamber. The model is used to analyse how the uncertainties on four input parameters are propagated through an aerosol dynamics model. The input parameters are: the rate of the reaction between SO₂ and OH (k₁), the ratio between the nucleation rate used in AERO2 and that derived from classical nucleation theory (t_n), the H₂SO₄ mass accommodation coefficient () and a measure of the turbulence intensity in the reactor (k_e). Uncertainties for these parameters are taken from the literature. One of the results of the analysis is that AERO2 and aerosol dynamics models in general can only predict upper bounds for the total number (N_tot) and total volume (V_tot) concentrations of the particles. The uncertainties on N_tot and V_tot are mainly due to the uncertainties on k₁, and t_n. An uncertainty factor of 20–100 still remains when the uncertainty on k₁, is reduced to ±5%. Aerosol measurements from three smog chamber experiments have therefore been used, in an attempt to reduce the uncertainty on k₁ and t_n. Values for k₁ are obtained in the reduced range 7.8 × 10⁻¹³ to 1.0 × 10⁻¹² cm³ s⁻¹, which is within the range found in the literature. For t_n, values in the range 10⁴–10⁷ are obtained, which is close to the upper bound of the range in literature. These values for t_n are in marked contrast with a recent set of experiments on nucleation in H₂SO₄-H₂O mixtures, which suggests a value for t_n of at most 10⁻⁵.     

Expected runtimes of evolutionary algorithms for the Eulerian cycle problem

Evolutionary algorithms are randomized search heuristics, which are applied to problems whose structure is not well understood, as well as to problems in combinatorial optimization. They have successfully been applied to different kinds of arc routing problems. To start the analysis of evolutionary algorithms with respect to the expected optimization time on these problems, we consider the Eulerian cycle problem. We show that a variant of the well-known (1+1)$(1+1)$ EA working on the important encoding of permutations is able to find an Eulerian tour of an Eulerian graph in expected polynomial time. Altering the operator used for mutation in the considered algorithm, the expected optimization time changes from polynomial to exponential.