An investigation was undertaken to develop a procedure for preparing molybdena-alumina catalysts for olefin disproportionation and to develop equipment and procedures for exploratory testing of the catalysts. A reproducible procedure for preparing molybdena-alumina catalysts was developed. This procedure consisted of impregnating Harshaw Al-0104-T, 1/8 inch alumina catalyst pellets with 10 to 30 percent aqueous ammonium molybdate solutions at 210 °F. The impregnated pellets were placed in the reactor, dried for three hours at 250 to 300 °F and were activated at 1000 °F for five hours. Dry nitrogen was passed over the catalysts during drying and activation. A reaction system was designed, constructed, and operated to perform exploratory tests on the catalysts. The reactor was constructed from 3/8 inch stainless steel tubing and packed with approximately 5.8 grams of catalyst for each test. The reactor was operated at pressures of 30 to 170 pounds per square inch, gage, at temperatures of 250 to 550 °F and at a weight hourly space velocity of 1.1 gram of feed per hour per gram of catalyst. The reaction products were analyzed by gas chromatography. The catalysts prepared during this investigation gave disproportionation of propylene to ethylene and 2-butene. Ethylene and 2-butene were formed in approximately equimolar quantities. Maximum conversion was found to occur in the temperature range from 300 to 400 °F. Conversion up to 30 percent was obtained using the catalysts prepared during this investigation. Limited data indicated conversion to be independent of pressure in the range of 30 to 170 pounds per square inch, gage. The catalysts were found to deactivate with time-on-stream. Due to the limited data taken, no quantitative conclusions were reached as to the rate of deactivation. / M.S.

Experimental resonant frequencies and mode shapes from vibration tests with a 1/5-scale model of the Titan III-A launch vehicle are presented, Measurements of longitudinally excited vibration modes of the model structure supported in a suspension system offering negligible restraint to longitudinal motion for five different propellant loadings are shown. The data indicate the quantitative and qualitative effect on the overall model vibration response due to different amounts of simulated liquid propellant in the tanks. The experimental data show the response of the model to be complex due primarily to structural coupling of modes. Two mathematical models are used to calculate the model vibration response; one represents a simple lumped-mass analysis and the other a more refined interpretation which considers axisymmetric shell, fluid, and mass components of the structure. Longitudinal vibration mode shapes and frequencies computed from the component model show better correlation with measured basic longitudinal structural. modes than those obtained using the lumped-mass representation. / M.S.

A taxonomic study has been made of two closely related races of Etheostoma flabellare flabellare Rafinesque, one from the Roanoke River of Virginia and the other from the Neuse River of North Carolina. They are compared in twenty-three characters (scalation, ray counts, and color marks). For eight characters, the Roanoke sample has been divided into its component groups (the Blackwater and Pigg river samples). These are compared to each other and to the Neuse sample. Four new characteristics are described. The shape of the line behind the eye is rated as rectangular or 8-shaped. The shape of the spots on the caudal fin is rated as solid or hollow. Three major color patterns are described; one of which is a juvenile pattern and the others are characteristic of males and females. In respect to belly scalation, three categories have been established which are dependent upon the extent of development of the scale row along the ventral mid-line. These are as follows: totally scaled, partially scaled, and naked. The Roanoke and Neuse fantail darters differ most in seven characters. These are as follows: total and pored scales lateral line, scales across belly, belly scalation, shape and number of spots caudal fin, and the persistence of juvenile color patterns in the adult Neuse female. Paedomorphosis, in the Neuse fantail, accounts for most of the major differences between the populations. / M.S.

While solutions to the nonlinear von Karman equations for large deflections of thin plates have been presented for annular plates under certain axisymmetric/loading conditions, little work has been done with unsymmetrical large deflections. In this investigation a systematic mathematical iteration technique is used to obtain a solution to the von Karman equations for an annulus fixed at the outer edge and which has a central rigid plug that is rotated about its diameter out of the plane of the plate. The linear, small-deflection solution to this problem presented by H. Reissner is used as the first approximation for large deflections. By using Reissner's solution for the lateral displacement to evaluate the nonlinear terms in one of the von Karman equations, a linear fourth order partial differential equation for the stress function is obtained. The particular solution to the stress function equation leads to multi·valued in-plane displacements, which are eliminated by proper selection of the homogeneous solution, The boundary conditions for the stress function equation are written in terms of the in-plane displacements, and wherever trigonometric functions of the small angle of rotation of the rigid inclusion appear, they are expressed in a power series of the angle and terms of higher order than the second power are neglected. By using the resulting stress function and the Reissner solution for lateral displacement to evaluate the nonlinear terms in the second von Karman equation, a linear, fourth order partial differential equation for the second approximation to the large deflection lateral displacement is obtained. Again the boundary conditions are expressed in a power series of the rotation angle and terms of higher order than the third power are neglected. The solution for the lateral displacement is a function of the first and third powers of the angle of rotation, where the part containing the first power is the Reissuer solution and the part containing the third power is a correction term reflecting a reduction in lateral displacement caused by the in-plane stresses. Thus by neglecting the third power of the small angle of rotation, the large-deflection solution reduces to the linear, small deflection solution. Any further iterations are not performed because the algebra involved becomes excessive; however, the iteration procedure can be repeated to obtain higher approximations. By taking appropriate derivatives of the stress function and the lateral displacement, expressions for the bending and membrane stresses as functions of the position in the plate and the angle of rotation are obtained. Numerical results are presented in graphical form for typical plates. Experimental data was obtained with an 18 inch outer diameter, 7.2 inch inner diameter, 0.0634 inch thick plate made of 7075-T6 aluminum. The results of the iteration solution are found to agree very well with the experimental data for lateral displacements up to one and one-half times the thickness of the plate, but the iteration solution begins to overestimate the nonlinear effect for larger displacements. As a limiting case to the title problem, an iteration solution for large deflections of a clamped circular plate loaded by a central concentrated moment is given. / Ph. D.

The Bays Formation is of late Middle Ordovician (upper Wilderness) age and ls a predominantly clastic formation that crops out in 16 belts in the southeastern side of the Appalachian Valley from near Roanoke, Virginia, to northwestern Georgia. The various lithotopes in the Bays include conglomerates containing limestone cobbles and quartz pebbles more than 1 inch across, sandstones, siltstones, mudstones, shales, and impure limestones. In most strike belts much of the formation is calcareous. The characteristic color of the Bays is "red”, but olive-gray, greenish-gray, and yellowish-gray are also common. Mud cracks are common in fine-grained Bays strata, particularly in the basal portion. The maximum known thickness of the Bays is about 1095 feet, in Monroe County, Tennessee. The Bays Formation in its maximum stratigraphic development is equivalent to the succession that includes the Bowen, Witten, Moccasin, and Eggleston formations of middle belts in the Appalachian Valley. The Bays at its type locality in the Bays Mountain synclinorium in northeastern Tennessee is underlain by the Sevier Formation and overlain by the Martinsburg Formation Several bentonites occur in the upper part of the Boys-Moccasin sequence and augment stratigraphic control. The presence of ghosts of glass bubbles and Y-shaped shards in tuffaceous rocks associated with the bentonites indicates a volcanic origin for the bentonitic material. The bentonltes (K-bentonites of some writers) are composed chiefly of illite, mixed-layer chlorite-montmor-illonite. Generally, clastic rocks in the Bays gradually decrease in grain size from southeast to northwest. The amount of calcium carbonate in Bays strata increases from southeast to northwest. This decrease in grain size and increase in calcium carbonate in the rocks toward the northwest also occurs in the Bowen, Witten, Moccasin, and Eggleston formations of middle belts in the Appalachian Valley. The increase in grain size of Bays sediments toward the southeast suggests that the source area of Bays sediments was in that direction. Sedimentary structures indicating current direction suggest that Bays sediments came from the south, southeast, and east. Rock southeast, and fragments in Bays strata include limestone, sandstone, siltstone, chert, orthoquartzite, metaquartzite, amphibolite, fine-grained metamorphics such as slate and phyiltte, and vein quartz. Nonopaque heavy minerals in Bays Strata include zircon, tourmaline, apatite, hornblende, zoisite, garnet, epidote, and corundum. These clasts and minerals indicate that Bays sediments were derived from older sedimentary rocks, low-grade and high-grade metamorphic rocks, and silicic igneous intrusive rocks. These data suggest that Bays sediments were derived from a rising crystalline land mass (or masses) to the southeast, possibly in the vicinity of the present Piedmont and adjacent Blue Ridge. A belt of Cambrian and older Ordovician sedimentary rocks, probably along the northwest side of the rising crystalline complex, was also exposed during at least part of Bays time and contributed to Bays sediments. It is believed that the great volume of Bays sediments necessitates a land mass source area larger than a volcanic island arc. It is beleived that local troughs on the Bays sea floor subsided faster than adjacent areas, and accommodated greater thicknesses of sediments. A few of these troughs may have also attracted slightly coarser sediments that bypassed less rapidly subsiding parts of the depositional basin. The rising of the land mass required to supply the large volume of coarse and fine Bays sediments and the volcanism that was important in the latter part of Bays time indicate considerable tectonic activity. The differential subsidence of the Bays depositional basin also suggests that Bays time was characterized by important tectonic activity in the southern Appalachian region. / Ph. D.

The purpose of this study was to derive industrial arts subject matter, suitable for use at the secondary school level, from the technology of microelectronics. This subject matter was to reflect the technology of the microelectronic industry and also be compatible with the objectives of industrial arts education. The study involved three major steps. The first step was the arrangement of information about the technology of microelectronics into groups of information denoted by conventional electric terms. In the second step, industrial arts subject matter was selected from the groups of information by using Olson’s “curricular components” as “categories of subject matter''. The third step involved the placing of the selected subject matter under the technical, avocational, and consumer functions of industrial arts. The sources of information about the technology of microelectronics were 312 periodicals dealing with the electronic industry for the years 1963, 1964, and 1965. The derived subject matter was presented in both narrative and topical outline forms. / Master of Science

Weed control in transplanted tomatoes with diphenamid, trifluralin, and paraquat was evaluated under field conditions on a predominantly Grosclose silt loan soil on the Virginia Polytechnic Institute Horticulture farm near Blacksburg, Virginia. The herbicides were used singularly and in certain combination at various rates and times of application. Diphenamid applied on previously cultivated soil at two weeks after transplanting tomato plants gave superior weed control with no apparent injury to tomato plants. However, the eame herbicide gave poor post emergence weed control and yield of tomatoes when applied after small weeds were present. Growth of tomato plants·was. suppressed by competition from weeds; however, ripening of tomatoes was accelerated as compared to untreated cultivated plants. Trifluralin applied pre planting also gave good weed control, but when applied post transplanting weed control was poor po•eibly due to incorporation technique. The higher rate of this herbicide seaweed a decrease in growth and yield of the crop. A mixture of diphenamid plus paraquat was effective on small weeds, but this treatment has less possibilities in commercial production as the spray cannot be directed to avoid contact injury to tomato plants. / Master of Science

In this work, four investigations of stratified flow were conducted in closed conduits, which included, l. numerical solution of velocity distribution by using a digital computer, 2. analytical solution and experimental verification of the internal surge wave velocity, 3. experimental observation on the mutual intrusion phenomena, and 4. experimental investigation of the internal hydraulic jump. An apparatus consisting mainly of a total length of 13 feet of transparent plexiglas pipe, two liquid pumps, a separator, two constant head tanks, a receiving tank, flow control valves, manometers, and discharge measuring devices, was built for the above investigations. The equation of motion was derived for the velocity distribution, starting from the Navier-Stokes equations. A special Poisson equation with a constant term on the right hand side of the equation was derived which was then reduced to a Laplace equation by a substitution. Considering appropriate boundary conditions, this equation was solved by a method of finite differences on an IBM 7040 computer. The method used in computation is solving a set of simultaneous equations by elimination. Less than two minutes machine time was required for a 39 by 39 matrix. Experimental results demonstrated fairly well the energy loss concept in surge wave considerations. The major energy loss at the wave front was assumed to be the expansion loss of the lower layer. The approximate solution holds for internal surge waves with small amplitude of any flowing area. A non-antisymmetric property was found during the mutual intrusion. That was quite contrary to the existing literature. No transient effect was apparent due to the limited length of pipe under investigation. An internal hydraulic jump was created by attaching a dam-shape barrier on the bottom wall of the pipe. A relation of conjugate depth ratio to the discharge ratio of the two phases was drawn by experimental results. / Ph. D.

The synthesis of a variety of polynuclear aromatic hydrocarbons by means of the condensation of grignard reagents with aromatic aldehydes did not always lead to the isolation of the desired diarylcarbinols. The delicate relationship between molecular structure and physiological activity demanded that only pure compounds of known structure be used in studying the carcinogenic and/ or carcinolytic effects of these aromatic hydrocarbons. Therefore, the above method of synthesis was eventually by-passed. But the apparently "abnormal" condensation of grignard reagents with aromatic aldehydes and the thermal decomposition of diarylcarbinols at high temperatures generated a great deal of interest from the mechanistic point of view, and these reactions were studied in detail in this work. The previously unreported ketones, 2-fluorophenyl 1-naphthyl ketone (52) and 2-fluorophenyl 2-naphthyl ketone (53), were prepared by the condensation of the cadmium reagents of 1- and 2-bromonaphthalene with 2-fluorobenzoyl chloride (51). Reduction of these ketones, 52 and 53, with a mixture of lithium aluminum hydride and aluminum chloride afforded the corresponding diarylmethanes, 2-(1-naphthylmethyl)fluorobenzene (56) and 2-(2-naphthylmethyl)fluorobenzene (57), respectively. Reduction of these same ketones, 52 and 53, with sodium hydroborate afforded the corresponding diarylcarbinols, 2-fluorophenyl-1-naphthyl carbinol (54) and 2-fluorophenyl-2-naphthyl carbinol (55), in good yield. The previously unreported 1-bromo-2-(1-naphthyl)naphthyl carbinol (45) was prepared by reduction of 1-bromo-2-(1-naphthyl) naphthyl ketone (44) with sodium hydroborate. This diarylcarbinol 45 was also prepared via the reaction of the Grignard reagent of 1-bromonaphthalene with 1-bromo-2-naphthaldehyde (41). The proof of structure of 45 was accomplished by studying the nuclear magnetic resonance and infrared spectra of 45 in conjunction with the nuclear magnetic resonance and infrared spectra of 1-bromo-2-(1-naphthyl)naphthyl carbinol-OD₁ (46) and 1-bromo-2-(1-naphthyl)naphthyl carbinol-CD₁ (47). The reported "abnormal" reaction of the Grignard reagents was investigated. The reaction of one equivalent of the Grignard reagent of 2-bromonaphthalene with one equivalent of 2-chlorobenzaldehyde gave the expected 2-chlorophenyl-2-naphthyl carbinol (37). The reaction of two equivalents of 2-chlorobenzaldehyde with one equivalent of the Grignard reagent of 2-bromonaphthalene gave 2-chlorophenyl 2-naphthyl ketone (36) by oxidation of the alkoxide complex formed by the initial condensation of the Grignard reagent with the aromatic aldehyde. The high temperature decomposition of diarylcarbinol 45 was found to lead to the formation of sym. -1-bromo-2-(1-naphthyl)naphthylmethyl ether (58). The structure of 58 was confirmed by molecular weight studies, infrared and nuclear magnetic resonance spectra and elemental analyses. The decomposition of ether at 58 240° was found to proceed slowly with the liberation of hydrogen bromide gas. Free radical initiators and hydrogen bromide gas were found to accelerate the decomposition of 58 at 240°. A reasonable mechanism has been postulated for the decomposition of 58 at 240°. The cleavage of ether 58 in the presence of hydrogen bromide gas would give rise to the formation of a secondary bromide, 1-bromo-2-(1-naphthyl)naphthylmethyl bromide (62). Homolysis of 62 would then give a bromine atom and a secondary free radical, 1-bromo-2- (1-naphthyl)naphthylmethyl free radical (63). The attack of free radical 63 on the benzylic hydrogen atoms of ether 58 is thought to be responsible for the formation of the diarylmethane, 1-bromo-2-(1-naphthylmethyl) naphthalene (48) and 1-brome-2-(1-naphthyl)naphthylmethyl ether free radical (64). Homolysis of 64 would then regenerate the secondary free radical 63 and the ketone 44. The coupling of two secondary free radicals 63, with subsequent attack of bromine atoms on the system, might give rise to the formation of di-[1-bromo-2-(1-naphthyl)naphthyl] ethylene (66). The attack of hydrogen atoms on 63 might lead to the formation of diarylmethane 48. Oxidation of ethylene 66 might give rise to the isolation of ketone 44. Evidence for these two reactions has been furnished by the vacuum distillation of secondary bromide 62. The attack of bromine atoms on the benzylic hydrogen atoms of ether 58 would give ether free radical 64 and hydrogen bromide gas. Homolysis of 64 would then give ketone 44 and secondary free radical 63. The decomposition of 58 would then appear to be cyclic in nature. The decomposition of diarylcarbinols 54 and 55 was judged to be free radical in nature, involving the formation of the two ethers, sym. -2-fluorophenyl-l-naphthylmethyl ether (67) and 2-fluorophenyl-2-naphthylmethyl ether (68), which decompose in the same temperature range as 54 and 55. Ethers 67 and 68 were not isolated. The decomposition of 67 and 68 was postulated to be a series of homolytic cleavages, giving rise to the formation of the diarylmethanes, 56 and 57, and the ketones, 52 and 53. / Ph. D.

An attempt was made to isolate L-N¹⁵-histidine from Escherichia coli cultured in a defined medium containing nitrogen-15 enriched ammonium salts as the only source of nitrogen. Commercially prepared L-N¹⁵-histidine.HC1.H₂0 was used to follow the limiting amino acid in the imbalanced diet in rats fed a chemically-defined imbalanced or corrected diet. Total nitrogen content and atom percent N¹⁵ were determined on the urine, gastrointestinal contents, diet, and the acid-soluble and protein fractions of the liver, kidneys, muscle, gastrointestinal tract, and serum at two, four, and six hours after the onset of feeding. The data were examined for changes in the concentration of N¹⁵ which might cause the imbalance phenomenon {reduced blood levels of the limiting amino acid). It was found that the limiting amino acid was not catabolized at an increased rate and that it was not absorbed or transported at a reduced rate due to the ingestion of an imbalance amino acid mixture. The increased efficiency with which the histidine was found to be incorporated into metabolically active proteins appears to be a primary cause of the reduced blood levels of the limiting amino acid and, therefore, of the imbalance phenomenon. Experimental verification was, therefore, obtained for the first unverified aspect of Harper's (12) thinking about the cause of the reduced appetite that is characteristic of the imbalance phenomenon. / Ph. D.