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.     

DANGERS OF LAB-PLANT SCALEUP FOR FILTERS INVOLVING SOLIDLIQUID SYSTEMS

Many laboratory procedures have been used for predicting the size of clarifiers, thickeners, filters, and centrifuges or choosing the optimum quantity of filter-aid and flocculants. Scaleup predictions are frequently based on experiments involving small pressure and vacuum filters, compression-permeability cells, and sedimentation rates. Among major problems related to the accuracy of scaleup are: (1) unrepresentative sampling, (2) aging of suspensions with accompanying changes in properties of cakes and sediments, (3) effect of sedimentation not included in theoretical equations, (4) wall effects in small diameter filters and cells, and (5) misapplication of theory to experiment.     

From a theoretical model to a predictive simulation model of operator interaction with support systems: designing experiments to build the numerical simulation

In this paper, we will discuss a methodology developed and applied in the European ITERATE project with the objective of designing experiments that will provide data to seed the numerical model of operator behaviour in different surface transport modes: road vehicles, rail transport and ships. The experiments aim to investigate how new technologies support different types of operators in different contexts. A structured approach was adopted. Firstly, an initial selection of the systems to be investigated was made, describing the support they provide for operators. Hypotheses were formulated on the effects of operator parameters on the interaction with the systems. A final selection of systems for the experiments was made, focusing on systems providing support for collision avoidance and speed management. The operator parameters (culture, attitude and personality, experience, driver state (such as fatigue) and the demands of the task) were operationalised and piloted. The next step was the development of scenarios to be implemented in a driving simulator. In the last step, the final experiments were designed and detailed.     

Oxidation of pyrite in coal to magnetite

When bituminous coal is heated in an inert atmosphere (He) containing small amounts of oxygen at 393–455 °C, pyrite (FeS₂) in coal is partially converted to magnetite (Fe₃0₄). The maximum amount of Fe₃0₄ formed during the time of heating corresponds to 5–20% of the total pyrite present, depending on the coal sample. The magnetite forms as an outer crust on the pyrite grains. The fact that the magnetic properties of the pyrite grains are substantially increased by the magnetite crust suggests that pyrite can be separated from coal by use of a low magnetic field. In a laboratory test, 75% removal is obtained by means of a 500 Oe magnet on three samples, and 60% on a fourth sample.     

Reaction of cholesterol 5,6-epoxides with simulated gastric juice

Cholesterol 5α,6α-epoxide (α-epoxide) and cholesterol 5β,6β-epoxide (β-epoxide) were individually suspended in simulated gastric juice (pH 1.2) at 37 C, and their reaction was followed by gradient high performance liquid chromatography (HPLC) with flame ionization (FID) detection. Both epoxides reacted rapidly in the aqueous acid medium. The α-epoxide formed 6β-chlorocholestane-3β,5α-diol (α-chlorohydrin) and 5α-cholestane-3β,5,6β-triol (triol), while the β-epoxide formed 5α-chlorocholestane-3β,6β-diol (β-chlorohydrin) and triol. The isomeric chlorohydrins reacted further to form the triol. In mildly alkaline aqueous medium, each chlorohydrin reverted to the epoxide from which it was formed. The data suggest that both epoxides, which have been reported to have adverse health effects in animals, would be largely hydrolyzed in the stomach and to the triol, which also has been reported to have biological activity. The data furher suggest that residual chlorohydrins surviving stomach residence can be expected to revert to epoxide in the more alkaline intestinal environment.     

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.     

Male european corn borer,Ostrinia nubilalis (Hübner), antennal responses to analogs of its sex pheromone

Experiments were conducted to (1) determine whether the electroantennogram (EAG) can detect differences among the responses of antennae from males derived from the three strains ofOstrinia nubilalis (Hübner), and (2) characterize the EAG responses of each strain to isomeric forms of the natural pheromone, (E)- and (Z)-11-tetradecen-1-ol acetate (TDA), and analogs possessing differences in the terminal alkyl group, cyclopropyl (CPA), ortert-butyl (TBA).EAG responses differed among the strains in two ways: (1) Antennae fromZZ males always produced an EAG to (Z)-TDA with an extended duration of response. This signature EAG response was found to be unique to the antennal response ofZZ males to (Z)-TDA, thus providing a relatively easy method of distinguishing liveZZ males fromEE orZE males. Correlated with this longer EAG response was a longer disadaptation time, i.e., the EAG response ofZZ antennae disadapted more slowly (ca. 10 min) than the response ofEE antennae. (2) Strain differences in the relative EAG amplitudes to isomers and analogs were observed at the stimulus amounts eliciting the peak EAG amplitude as follows: TDA CPA > TBA forZZ males and both isomers; TDA > CPA TBA and CPA TDA > TBA forEE males and theE andZ isomers, respectively; CPA > TBA TDA forZE males and both isomers. Dose—response relationships were seen for all compounds if amplitude (peak height) of the EAG was used as a measure of response. However, if width of the EAG at half the peak height (peak width) was used, then only theZZ antennal response to (Z)-TDA resulted in a meaningful dose-response relationship. For all strains, the EAG amplitudes elicited by theZ isomers of any of the tested compounds were greater than those elicited by the correspondingE isomers. Therefore, correlations between the relative EAG and upwind flight responses were observed in theZZ (r = 0.86) andZE (r = 0.80) strains but were not correlated in theEE strain (r = 0.18). Temporal studies showed that adaptation, not postexcision deterioration, was responsible for the observed decreases in the EAG amplitude after repetitive stimulation or after stimulation with amounts in a descending order. Disa-daptation required at least 20 min for a moderate dose (10 g for 1 sec). Developmental studies showed that antennae from 2-day-old adults had the greatest EAG response.     

Thermal stability of substituted phenol-formaldehyde resins

A variety of crosslinked phenol-, or derivatized phenol-formaldehyde polymers have been synthesized. The phenol derivatives included o- and p-cresol, p-nonylphenol, m-pentadecylphenol, and raw and distilled cashew nutshell liquid. The derivatives were copolymerized with phenol and formaldehyde using sulfuric acid as catalyst to yield novolak-type prepolymers, which were then cured with hexamethylenetetramine. Thermogravimetric analysis was used to evaluate the thermal stability of the cured resins. It was found that the thermal stability of the resins decreased with increasing amounts of cashew nutshell liquid, with distilled cashew resins being slightly more thermally stable than raw cashew resins. The thermal stability of resins containing substituted phenols with alkyl chains was observed to increase from n-pentadecylphenol to cresol to phenol. The trend in thermal stability of the resins may be explained on the basis of alkyl groups being less thermally stable than aromatic rings. The amount of hexamethylenetetramine used to cure the prepolymers also influences the thermal stability of the resins. It appears that a level of 10 to 15% hexamethylenetetramine maximizes the thermal stability of the resin.