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By G. P. Conard, E. H. Rennhack

The generation of fibers composed of individual TiZn15 compound particles and their influence on crystallographic orientation in chill-cast, hot-rolled hypoentectic Zn-Ti alloys were explored. Metallo-graphic examination and X-ray diffraction data show that such fibers form a planar network after 50 pet reduction which eventually tends to suppress twinning at some critical reduction level (-90 pct) where the grain size approaches the interfiber, spacing. This leads to the development of a duplex-type projerred orientation through slip rotation consisting of an al-most ideal (0001)(2iiOj texture and a (0001) (1010) rotated component. Correlations between basal-plane rotation and secondary- creep rc11e sugg-est, however that prejerred orientation does not contribute in a major way to the creep resistance of these alloys. EFFORTS to improve the creep resistance of zinc through alloying without incurring a loss in fabricating properties have achieved only minor success with the exception of the very effective addition of titanium. Anderson, Boyle, and Ramsey,l for example, demonstrated that increasing the amount of thiselement from 0.05 to 0.23 wt pct produced a progressive, 45-fold increase in the inverse creep rate of hot-rolled

Jan 1, 1967

"The Tooele plant is situated at the mouth of Pine Canyon, five miles northeast of Tooele City. The site forms one terminus of the Tooele Valley railway, which runs southwest through Tooele City to Warner, a station on the Los Angeles and Salt Lake Railroad, thirty-five miles southwest of Salt Lake City.An aerial tramway, four miles in length, crosses the Oquirrh Mountains and connects the plant with the Bingham district.The plant consists of a lead-zinc flotation concentrator, lead smelter and copper smelter.SAMPLING MILL The mill is a standard Taylor and Brunton sampling mill, built in two sections, each with a capacity of 100 tons per hour. The building is of steel and concrete, 40x84 feet. A well-equipped pulping, sampling and drying room is attached.All ore is sampled here and then distributed by conveyors to cencentrator, lead smelter and copper smelter bins.CONCENTRATOR This flotation mill is arranged in two units of 500 tons capacity each, one equipped with Callow pneumatic flotation cells, the other with Mineral Separation sub-aeration machines.The feed is maintained as uniform as possible by bedding, after coarse crushing at the sampling mill. Standard practice of ball mill grinding and classification is followed."

Jan 1, 1925

By T. Lane Carter

BEFORE describing the experience with the Chinese on the Rand and the work they have accomplished, it will be necessary, sary, first, to give a brief account of labor-conditions in the Transvaal since the war, and then to show how the necessity of importation of labor arose. As is well known, the Transvaal mines are run on the dual system of labor-that is, the rough work is done by colored laborers under the superintendence of white men. From the start of mining operations in South Africa there has been the cry of shortness of native labor, due in great measure to the failure of Kaffirs to work continuously in the mines. While he works, the Kaffir is a satisfactory laborer, but his period of service is short, averaging about nine months. People unacquainted with the Kaffir have maintained that, by offering a higher wage and better accommodation, better results would be obtained from the native workers, but an increased wage simply aggravates the trouble. The Kaffir's wants are few. While at work he spends little of his money, and before long has sufficient capital with which to buy wives and become a gentleman of leisure. Doubling the wage of the Kaffir means that he acquires a competency in half the time, so that his period of service is correspondingly reduced. In 1899, before the war, there was always a cry about the scarcity of Kaffir labor. The highest number of natives at work was in July and August, 1899, when nearly 100,000 were employed. At the outbreak of hostilities the Kaffirs were scattered far and near, many doing well during the war by working for the military authorities. On the, resumption of mining operations on the Rand a serious mistake was made. Based on past experience, it was argued that if the whole industry decided to start anew with

Sep 1, 1908

By J. Bruce Wagner, Roger L. Levin

Lattice-parameter measurements have been carrzed out at room temperature on undoped and on chromium-doped wustite as a function of oxygen concentration. Results may he expressed by for the undoped uustite. These data are in agreement with and extend the work of' Jette and Foole. The present results are consistent with the cation vacancy model. for metal- deficil wuslite, both undopen and doped. SEVERAL investigators have made room-temperature lattice-parameter measurements on wustite as a function of composition. Jette and Foote used these measurements to determine the phase limits of wustite. Willis and Rooksby and Benard have also measured the lattice parameters of wustite at room temperature, but their values of a. vary considerably from those of Jette and Foote. In conjunction with Studies' on the transition from surface-controlled heterogeneous reactions involving CO-C02 oxidation of metals, lattice-parameter measurements on undoped and chromium-doped wiistite have been performed. These studies are especially needed to clarify conflicting data of previous authors, to extend the data to the stability limits of wiistite as determined by Darken and urr,6 which include a larger range of existence than that found by Jette and Foote, and to test by X-ray means the role of chromium as a vacancy producer in wiistite.

Jan 1, 1967

By R. S. Shoemaker, D. L. Harris

Past investigations into the possibility of concentrating the low-grade iron ores of the Gogebic Range in Wisconsin have been hampered by the complex association of the constituent minerals. In part the problem arises from the fact that the iron occurs essentially as two minerals, hematite and goethite, having nearly the same chemical composition but exhibiting different physical properties. Individual grains of these minerals are usually so small that the ore must be ground to a size finer than 325 mesh if substantial liberation of the minerals is to be secured. Appraisal of beneficiation tests on this iron ore requires, therefore, some method of determining quantitatively the contents of constituent minerals in the various products of the beneficiation. Because of the chemical similarity of the two iron minerals, chemical analyses do not provide a means of differentiation. Although the minerals are different physically, they are both opaque and friable, and as the ore must be ground to a very fine size for liberation to be secured, quantitative microscopic methods of analysis are extremely difficult at best. In an effort to overcome these analytical problems, a quantitative X-ray diffraction analysis method has been developed at the University of Wisconsin for the research program on iron ore beneficiation.

Jan 5, 1955

By P. A. Beck, A. H. Lutts

IN the classical picture of recrystallization the growth of strain-free grains at the expense of a strained and work hardened matrix is responsible for the softening of cold worked metals on annealing. It has been commonly assumed that the release of the stored energy of cold work, softening, and re-orientation take place simultaneously, as the high angle boundaries of the new recrystallized grains sweep over the cold worked matrix. However, recent evidence indicates',' that, at least in some cases, considerable or even complete soften- ing may take place essentially without reorientation (i.e., without the migration of ordinary high angle grain boundaries, or "recrystallization'') and the release of most of the stored energy of cold work may precede softening. These cases suggest that the property changes, taking place during the annealing of cold worked metals, may be associated with various distinct processes. The study of such situations is of considerable interest, since quantitative data are still scarce. In the present work, isothermal softening curves were determined for a heavily rolled aluminum single crystal, under such conditions that no "recrystallization" occurred until after complete softening. The hardness data were correlated with X-ray diffraction pinhole patterns in order to detect any reorientation that may occur and with measure-

Jan 1, 1955

By K. V. Hoover, D. M. Lapham

In Pennsylvania, 310 sampled sites of clay and shale have been studied with regard to potential use, lithology, physical properties, fired properties, major-element chemical analyses, and quantitative five-component X-ray mineralogy. Approximately 80% of the samples are of some potential use. Binary correlations of test data vs. potential use indicate that certain empirically determined parameters may be critical. These are: lithology, particularly for medium to superduty refractories and lightweight aggregate; kaolinite content for refractories vs. low-temperature fired product sources; quartz analyses with an apparent necessary minimum quantity for brick; quartz content, which is low in high grades of lightweight aggregate; mica content, which is low for refractories and possibly high for lightweight aggregate; total iron, which is low for refractories and shows a 4.0% minimum for lightweight aggregate; carbon dioxide, which is low for refractories, beneficial in lightweight aggregate, and probably restrictive for some tiles; chlorite-vermicalite, which is low for refractories and possibly beneficial in lightweight aggregate. In Pennsylvania, clay and shale materials constitute one of the state's major economic mineral resources. To date, the testing program indicates considerable development potential in brick, tile, and lightweight aggregate industries and perhaps a future potential for aluminum from shales that exceed 20% AID..

Jan 1, 1972

By Carleton Ellis

(Presented at a meeting of the New York Local Section of the Institute, Apr. 12, 1912.) I. INTRODUCTION. THE problem of the influence of hot surfaces upon gaseous combustion is one which, from a purely scientific stand-point, has engaged, for many years past, the attention of Prof. William A. Bone, of Leeds University and the Imperial College, London; and as his recent work has been the direct outcome of earlier scientific investigation, it will be appropriate, by way of introduction, to review briefly the present position of science with respect to this important subject, as stated by Professor Bone. One may perhaps best arrive at an understanding of the term " ?flameless " or " surface " combustion by considering certain facts which differentiate it from the more familiar processes of combustion as they occur in ordinary flames. All hot surfaces have an accelerating influence upon chemical changes in gaseous systems. If, at any temperature, a gaseous system, A, tends to pass over into another system, B, contact with a solid at the same temperature will accelerate the process. To take a very simple example, if a mixture of hydrogen and oxygen in their combining proportions (electrolytic gas) were maintained in an inclosure with smooth glass walls at a temperature of, say, 450° C., there would certainly be a tendency to form steam, but the rate of change would be negligibly small. If, however, there were brought into the system some porous solid material at the same temperature, so that a large surface was exposed to the gases, the rate of change would at once be rapidly accelerated in the layer of gas immediately in contact with the hot surface. Steam, the product, would diffuse outward from the surface, and the supplies of hydrogen and oxygen at the surface would be renewed by diffusion inward. Thus combustion would proceed heterogene-

Sep 1, 1912

By R. J. Quigg, G. P. Conard, J. F. Libsch

IN a recent investigation of the Mn-Ge system by Zwicker it was reported that two inter-metallic compounds in this system, Mn,Ge, and Mn,Ge,, exhibited ferromagnetic properties. Of these, Mn,Ge, was reported as "strongly magnetic" and Mn,Ge, was said to be "weakly magnetic" but no actual values were given. In a study of magnetic alloys of nonmagnetic elements sponsored by the United States Army Signal Corps at Lehigh University, test bars having the nominal composition of these compounds were prepared by pressing elemental powders and sintering them in a purified helium atmosphere. Magnetic values obtained on these compounds are reported in Tables I and 11. It should be cautioned that the test bars were somewhat porous and that X-ray patterns run on these materials indicated that the homogenization in the samples was not complete, but that in each case the compound reported on was the dominant phase. The (B-H) max and particularly the Br values for pure dense M&Ge, can, therefore, be expected to be somewhat higher than those reported herein, while those for Mn,Ge, may be in error in either direction. Further details on this investigation are available in previous publications.23

Jan 1, 1956

By Ralph Hultgren

A CONSIDERABLE interest in the subject of superlattices has been mani-fested by many papers and reviews that have recently appeared, both in physical and metallurgical publications. This interest is due largely to the apparent simplicity of the ordering process, which permits the explana-tion of many phenomena on the basis of elementary theory. Moreover, ordering may cause important changes in the physical properties of alloys. In this paper, we shall discuss the causes of superlattices in terms of simple properties of the elements that give rise to them, together with a series of experiments performed to test our conclusions. Evidence is presented that in some cases the process of ordering is more complex than might be supposed. While the different species of atoms are usually found in random posi-tions in alloy lattices, in some cases unlike atoms tend to be nearest neighbors. Bethe'st "order of neighbors" is a statistical measure of this tendency. At suitable compositions it is possible for atoms in large regions to be regularly arranged, which causes superlattice lines to appear in X-ray diffraction patterns. Bragg and Williams2 have dealt with this "long-distance order" in their fundamental work on superlattices. Excellent discussions of superlattices are to be found in current reviews.3,4

Jan 1, 1939

By Evan Evans

IT is appropriate to evaluate 1947 in review as a year of a peacetime record production of about 676,000,000 tons of coal (anthracite and bituminous), closely approaching the extraordinary wartime output in 1944. Considering the general price-wage inflation, it is in point to note that the coal industry sustained the highest wages paid to workers in any major industry, but that coal prices at wholesale levels have risen much less percentage wise than the average for all commodities. The sellers' market continues to prevail. In addition to serving our own country's enormous needs, our coal industry is exporting extraordinary tonnages overseas. This unusual export demand is likely to continue for a while. Moreover, the demand in Europe for American coal mining machinery is a real tribute to the management efficiency of our modern mechanized coal industry. Competitively, the petroleum industry is concerned over its long-term supply, and already a synthetic fuels industry is being publicly advocated. In due time coal and lignite are bound to be

Jan 1, 1948

By G. R. Purdy, J. G. Parr

The intermetallic compound Ti2Co was studied by X-ray diffraction and metallographic techniques. The phase occurs off stoickzometric composition, with its greatest variance at high temperature. The solubility limits of the phase have been cletermined, and an amendment to the titanium-cobalt phase diagram is suggested. THE first intermetnllic compound to appear at the titanium-rich side of the titanium-cobalt system was found by Laves and wallbauml to be Ti2Co. They described this compound as isomorphous with Ti2Ni and Ti2Fe, and demonstrated that it had a face-centered-cubic structure with 96 atoms per unit cell. This contention is supported by the work of Duwez and Taylor2 and Orrell and Fontana3 who also determined the lattice parameter to be about 11.30A. Rostoker4 believed that Ti2Co did not exist, and that the phase considered by the other workers to be Ti2Co was Ti,Co20. However, Orrell and Fontana determined oxygen and nitrogen contents and found that their alloys did not contain sufficient of these elements to produce significant quantities of a stoichiometric oxygen compound. The present investigation was initiated to determine the composition limits of the phase Ti,Co.

Jan 1, 1961

By G. R. St. Pierre, R. D. Blackburn

Oxygen contents of' liquid-iron alloys saturated with oxides are analyzed. Minimum points observed in particular Fe-X-O systems can be predicled by a simple extension of first-order interaction methods. If minimum oxygen content occurs at N; where r is the ratio of metal to oxygen in the oxide phase. RECENTLY, wisher' reported on solubility measurements of A1203 in liquid iron at 1580°C which support the earlier work of d'Entremont, Guernsey, and chipman2 and Gokcen and Chipman. Swisher's diagram is reproduced in Fig. l. Minimum points in oxide solubilities have also been found in the Fe-Cr-0 system,4 Fig. 2, and the Fe-Ti-0 system,' Fig. 3. Minima positions can be used to confirm approximately the measured first-order interactions, &, cgr, and E&~, in liquid iron and to deduce compositions of components of constant activity in the oxide phases. Consider the solution of Alz03 in liquid iron: for which an equilibrium constant can be written as: differentiating Eq. [2] with respect to Na~, the atom fraction of &l in the metallic solution, and noting that If the activities of Al and 9 are expanded by a first-order interaction model, then:

Jan 1, 1969

By R. B. Brinsmade

The following is an attempt to form a formula by which a mine can be quickly evaluated, aft,er all pertinent physical data have been collected from observations on the ground by a competent mining engineer. Assumptions. Let Q = price to be paid for the mining property. M = cost of developing the mining property to yield y tons of ore daily. P = cost of suitable plant to treat y tons of ore daily, p = value of said plant when the mine has been exhausted. C = total fixed capital investment. W = working capital investment. Then let C + W = total capital investment. y = required yield of ore daily in tons. Y = yield of ore yearly in tons, d = number of producing days per year, u = average operating profit per ton of ore. R = rate of interest to be earned on total investment of (C + W). r = rate of interest to be earned on sinking fund annuity. v = tons of positive ore available in mine. x = tons of probable ore available in mine, z = tons of possible ore available in mine, m = fractional factor to change probable to positive ore. n = fractional factor to change possible to positive ore. Q = tons of total ore available in mine. t = time in years to exhaust mine at rate Y.

Jan 1, 1909

By A. H. Tousley

Current problems in the cement industry are discussed and suggestions for solving them by modernization are made. Cement facility modernization is discussed in considerable detail with examples illustrating before and after conditions. Itemized are the improvements realized in better working conditions, better efficiency, higher production, lower costs, and better community relations. These improvements are related to the overall profitability of the particular plant or facility.

Jan 1, 1972

The following petition for amendment of the constitutional provisions relating to qualifications for membership in the Institute, signed by 75 members, of whom 27 are members of the Committee on Increase of Membership, was received by the Board of Directors, was printed on the program of the New York Meeting sent to all members early in January, and is now being voted upon by the membership: In accordance with the terms f Article X, we hereby propose the following amendment to the Constitution, Article II, Section 2: Members shall comprise all those persons who on the third Monday of February, 1918, were members of the Institute, and in addition thereto, all those thereafter, elected or transferred into the, class of Members. A person to he eligible for election or transfer into the class of Members must he at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. Graduation from the scientific course of a college, approved by the Committee on Membership, shall be considered equivalent to two years' employment, as required in the previous sentence.

Jan 2, 1918

By K. D. Jacob

IN the decreasing order of the tonnages involved, the uses of phosphates can be grouped conveniently into three general classes, namely, fertilizer; chemicals for military, industrial, and technical purposes; and mineral feed for livestock. The quantity of phosphate used as fertilizer, principally in the form of superphosphate, has always exceeded by far that used for all other purposes, though in recent years a marked increase has occurred in its consumption for the other two general classes of uses. Prior to the present century large quantities of superphosphate, as well as a considerable portion of the production of phosphorus chemicals, score made from bone materials which were plentiful and cheap in some areas and which could be more easily processed than phosphate rock for the manufacture of chemicals. Today, however phosphate rock has almost completely displaced bone as a raw material for the manufacture of chemically processed phosphates in nearly all countries of the world.

Jan 1, 1944

By K. D. Jacob

MONTANA Phosphate Produucts Co., a subsidiary of The Consolidated Mining and Smelting Co. of Canada Ltd., operates three properties near Garrison, Mont., known as the Anderson, Graveley, and Luke mines. All three are underground operations, mining the same narrow bed at points several miles apart. The Anderson, the oldest and largest of the three, has produced about 700,000 long tons since 1929. The Graveley has produced slightly over 100,000 long tons since 1940, and the Luke, acquired in 1943, is still in an early stage of development. The great bulk of the output has been shipped to the Trail, B. C., plant of Consolidated Mining and Smelting Co. for use in the manufacture of fertilizers. The phosphate seam is the basal member of the Permian Phosphoria formation. In all three mines it has a uniform thickness of 3 to 4 ft. of oulitic phosphate, with a few shaly partings. The overlying part of the formation comprises about 50 ft. of chert and the immediate footwall consists of a few feet of shale and sandstone. underlain by the Quadrant quartzite.

Jan 1, 1944

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.'-'2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;' 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;'" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-' of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963