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By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.' Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By S. M. Marshall, B. M. Bird

For a number of years European investigators have used laboratory methods of predicting the probable strength of coke made from coal, and recently several investigators in the United States have reported the use of various tests for this purpose. There is at present no method accepted as standard, however, nor is there even agreement as to the general type of test that should be used. Furthermore, because the details of most of the tests have not been worked out carefully, one investigator can not hope to duplicate the work of another. The extension of coke manufacture to new localities in the United States, and the increasing need for cokes of exceptional qualities made from the most economical mixtures, made it desirable to have some simple laboratory test which will determine whether given coals, alone or blended with other coals, are more satisfactory from the standpoint of coke strenpth- than others of different cost. The work described herein has resulted in the development of a simple laboratory test which, it is believed, can be generally adopted in coal laborat,ories, and which will give concordant results even though performed by different investigators in different laboratories. The general method of predicting whether a coal or a mixture of coals will produce a strong coke, resistant to crushing and shattering, has been to correlate the known strengths of the cokes produced in commercial ovens with some measurable constituent or with some property of the coals, and then to use the relationship so found for forming an estimate of the coking strengths of coals unknown. Several such correlations have utilized the percentages of the various ultimate constituents of coal, such as the oxygen content and the hydrogen-oxygen ratio;(39)§ other correlations have involved the proportion of a, B and r com-pounds, (17,21,30c) or of "oil and solid bitumens."(16,30) Also a relationship has been traced between the coking properties of coal and the rate of change of the resistance offered to the flow of an inert gas by fine particles of the coal while being slowly heated. (11,176) But the most general corre-

Jan 1, 1930

By L. C. Morganroth

Magnesites are of two general classes - massive and crystalline.

Jan 1, 1915

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By Dudley L. Davis, E. C. Peterson

Introduction The Darwin District is 30 miles east of Olancha which is 220 miles north from Los z4ngeles via U. S. Highway No. 6. The ore deposits occur in the Darwin hills that have been elevated above the Darwin plateau by typical basin and range-type faults. Some of these faults have been active quite recently as shown by the displacemerit of Quaternary (?) basalt flows and the rejuvenation of erosion in Darwin wash. The ore bodies occur as fissure fillings and replacement of favorable beddings in a thick series of Paleozoic limestones, dolomites, shales and quartzites. Rich oxidized lead-silver ores were dis'Overed in the early seventies. BY 1875, Darwin had a population Of about 5000, and by 1880 several small mills and smelters had been built. Early exhaustion of surface ores, the isolated location of the district, and fluctuation Of metal prices caused intermittent operations until World War 11. The district production is estimated at about $3,000,000 prior to 1900 and perhaps $4,000,000 between 1900 and 1945 when Anaconda purchased the major producing mines. 'or the Past two Years, daily production has averaged 75 tons of direct shipping and 150 tons of milling-grade ore. At present, 300 tons of mixed oxide and sulphide ore are treated by flotation, the oxidized lead minerals being activated by addition of sodium sulphide after galena and sphalerite have been recovered from the circuit. Extraction averages 85 pct of the lead, 80 pct of the silver, and about 33 Pct Of the zinc in a bulk concentrate. The mill is designed so that minor changes permit selective flotation of pyritic lead-zinc ores encountered at depth. General Geology The oldest rocks in the Darwin hills are a series of Paleozoic limestones, dolomites, shales and quartzites probably pennsyl-vanian in age. These rocks have been intruded on the Rest by the Coso granite batholith and on the east by a granodiorite stock. Numerous sills and dikes grading from orthoclase granite to gabbro are exposed in the underground workings. The sedimentary rocks have been considerably folded and faulted, the most prominent structure being a northwest pitching anticlinal fold, the crest of which lies just west of the ridge line of the Darwin hills, The east limb of this fold has been intruded by the granodiorite stock and east of the stock the sediments show several closely spaced anticlines and synclines. The minor flexures on the west flank of the major fold are structurally important in localizing the ore in the Defiance and Essex mines of the Darwin group. There are three principal systems of faulting and fissuring, most of which are post-intrusive and premineral in age, with minor amounts of postmineral movement. The Darwin tear fault is the largest, most persistent fault in the district. It strikes N 60 to 75°W, dips steeply south and is traceable for about 10 miles. It is a normal

Jan 1, 1949

By William N. Poundstone

What attracts young engineering graduates into the coal industry? What do these young men expect of a career in coal mining? These questions are often asked and debated by mining men throughout the country. In order to present a comprehensive answer to them, an opinion survey was conducted at West Virginia University's School of Mines among the junior and senior classes and part of the sophomore class. The tabulation of the answers showed that the present-day mining engineering student is an older, more mature individual as compared with former years and as compared with other present-day college students. The average age of the country's record-breaking 150,000 college graduates is 24 years. Among this year's mining graduates at West Virginia University, 78% are of this age or older. Over half (54%) of those polled in the survey are married. This is com- pared to 30% as a national figure. Of those married, 38% have one child and over 6% have two children. The entire senior group covered by this survey has averaged almost three years in the armed forces. An article entitled "The Class of '49" in the June issue of Fortune magazine states that this year's class is the oldest, most mature class in history. Our survey indicates that the mining engineering students at West Virginia University are well above the average in this respect.

Jan 1, 1949

By AIME AIME

M ODERN metallurgy properly belongs to this century. The great advance made in this science is directly attributable to the discovery of the Roentgen rays. Application of the results of this discovery, together with the more recent corroborating studies in electronic diffraction have definitely and for all time established this science. Metallurgists today speak with familiarity of the atoms of the different metals in terms of their orientation, atomic volumes, lattice structures, dimensional lattice constants distance of nearest approach, and the like. One matter of profound interest, which is quite staggering to the imagination of the human mind, is the enormity of the number of atoms even in a small particle of metal. As an illustration, let us compute the number of atoms in the volume of one cubic centimeter in a single grain of absolutely pure copper. Eighteen and a fraction cubic centimeters equal the volume of one cubic inch.

Jan 1, 1940

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By F. C. Canney

Geochemical prospecting seeks hidden mineral deposits by sampling for variations in the chemical composition of naturally occurring materials. Usually the samples are of soils and other products of weathering and erosion—surface materials extremely susceptible to contamination by human activities. Except when a survey is conducted well away from populated areas, contamination is an ever-present hazard. The program's success is particularly endangered when the contaminants are the elements sought; if these occur erratically throughout an area, spurious anomalies completely unrelated to mineralized areas can be formed. Evenly distributed contamination can be dangerous too, if it raises the background to such a level that true anomalies can no longer be easily detected. Suppose, for example, that in an area where the lead background is 20 parts per million the soil over a lead vein contains 1000 ppm of lead. Here the contrast would be 50 to 1, which is very satisfactory for geochemical surveying. Now if 1000 ppm of lead from some source were added evenly to the soil in this area, the contrast would be reduced to about 2 to 1, and the anomaly would no longer be readily detectable because a threshold of significance twice the value of the background is the minimum generally used for interpreting geochemical data. Of the many possible sources of contamination, probably most important are smelter fumes, which may distribute large quantities of metal contaminants over many square miles of ground. For several reasons, the investigation reported here was begun in the Coeur d'Alene district in northern Idaho: 1) a lead smelter has been operated in this district since 1917 and an electrolytic zinc plant since 1928, and presumably the contamination patterns are strongly developed; 2) to evaluate the usefulness of certain geochemical techniques, V. C. Kennedy and S. W. Hobbs of the USGS had already studied the distribution of copper, lead, and zinc in the soils (both in background areas and other veins) and in the water and plants, providing a criterion for measuring the magnitude and effect of soil contamination; 3) one of the economically important parts of the district lies south of the South Fork of Coeur d'Alene River and within a radius of five miles of the reduction plants near Smelterville (Fig. 1). In this area, and in the entire district, conventional methods of prospecting are hindered by heavy vegetation and thick soil cover, and the possibility of contamination by smelter fumes has discouraged geochemical prospecting. Should data reveal that geochemical prospecting could be done successfully in such an area, a particularly useful tool would be available to mining companies and prospectors searching for concealed orebodies in this economically important part of the district. The field work on which this report is based was done from July 28 to 31, 1955. It should be emphasized that this was reconnaissance study only, and therefore far from exhaustive. Previous Investigations in U. S. : The first geochemical survey known to have been affected by contamination was conducted in 1940—a geobotan-ical reconnaissance made in the Michigan copper district by a private company. Geologists found striking variations in the copper content of oak and maple leaves, but unfortunately the high copper isograds of the study seemed to be related more to the Calumet and Hecla copper smelter fall-out than to mineralized ground.' The leaves of one oak tree near the smelter contained 0.4 pct Cu. Similar contamination was reported by Clarke (Ref. 2, p. 41), who conducted experimental geochemical soil and botanical surveys at Ray, Ariz. He found that the leaves of oak trees growing in unmineralized ground near Superior, Ariz., contained more copper than the leaves of oak trees growing on the capping of the Ray orebody and attributed this fact to contamination from the fumes of the Magma smelter at Superior. According to H. E. Hawkes,3 soils and stream sediments in the Superior area are also severely contaminated. Hawkes' work there has shown a copper content averaging 0.5 pct in the surface horizons of soils within one mile of the smelter stack. Samples taken only a few inches below the anomalous surface samples showed only background copper values. In 1950 L. C. Huff' of the USGS made a geochemical survey in an area near Jerome, Ariz., and found considerable zinc and copper in the soils over unmineralized basalt close to Clarkedale, Ariz., and over limestone close to Jerome. As the amounts were notably greater than could reasonably be expected to be derived from the underlying rocks, Huff suspected airborne contamination from the smelter at Clarkedale. Description of Area: The area sampled in detail (Fig. 1) for the study presented here is one of strong relief. The dominant watercourse is the westward-flowing South Fork of the Coeur d'Alene River. East of Kellogg the South Fork flows in a rather narrow canyon, but its valley floor widens considerably to the west where much of the flood plain is covered by an extensive veneer of mining, milling, and smelting debris. South of the South Fork and between Big Creek and Pine Creek is a mountainous area where

Jan 1, 1960

SUDBURY ore processed by International Nickel Co. of Canada Ltd. was recovered for many years as two mill concentrates, one primarily of copper, and the other mixed pentlandite-pyrrhotite, But, Since iron content of the nickeliferous pyrrhotite concentrate was ten times its nickel value, capacity of smelting was limited by the need for slagging the excess iron. A process for recovering the iron con- tent was developed after some years of research and a $20-million plant was constructed to employ the new method. Built near Copper Cliff, Ont., the plant started operation early in 1956, scheduled for separate treatment of 365,000 tons of pyrrhotite each year. It is only the first unit of an installation which will have a capacity of more than 1 million tons per year of pyrrhotite. By early 1958, production totaled more than 200,000 long tons of 68 pct Fe pellets containing 0.003 pct P, 1.5 pct SiO2, 0.01 pct S, and 0.15 pct Ni.

Jan 8, 1958

By Goerge F. Weaton

Since 1909, when an agreement between Minnesota's Tax Commission and the University of Minnesota's School of Mines was worked out, it has been the annual responsibility of the School to evaluate and classify the iron ore deposits within the State. These unique duties of an academic institution have provided School officials with an excellent view of the past, present and probable future of the mining industry in Minnesota as the average grade of iron ore (excluding taconite) * diminishes while at the same time it competes with beneficiated taconites and foreign high-grade ores for use in America's eastern blast furnaces. SYSTEM OF EVALUATION In the latter part of November of each year, the Mining Division of the Department of Taxation makes a preliminary study of the active mines which the Department wants the School of Mines to review. These are discussed with the engineers of the Ore Estimate Division of the School of Mines and with the mining companies. After these discussions, a list of the mines of each of the major operating companies is submitted to the Ore Estimate Division of the School of Mines with the request that these properties be reviewed by them as of the next assessment date (May 1st). At the same time, a letter is sent to the mining companies requesting that they submit to the Division their own estimates on the selected mines operated by them, together with all computations, drill records, maps and cross-sections. The mining companies are re- quested to send in this information during the first half of the year, and, as far as is possible, they have always complied with this request promptly. Much of this information received by the School of Mines is of a confidential nature and is treated as such.

Jan 1, 1965

By John N. Dew, William L. Martin, `

This paper describes the results of a laboratory investigation conducted to obtain data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. Air and fuel requirements, rates of advance, com-bustion temperatures, and coke and fluid distributions are presented. The mechanism of oil recovery by in stiu combustion is discussed. Five crude oils ranging in gravity from 10.9 to 34.2"' API were prodrrced from a semiadiabatic, uncon-.solidnted sand pack by in situ combustion. Experimental conditions were varied over a wide range in order to determine the inter-relation-.ships of process variables. The mini-mum air flux requirement for self-sustained combustion was found to he less than 10 scf/hr-ft'l. The rate of advance of a self-sustained combustion zone was found to be nearly proportional to the air flux at the combustion front. The effects of presrure and injected air flux were studied in a series of experiments using a 21.2" API crude. A minimum air require-ment was observed at an air .flux of 20 scf/hr-ft'. The oil saturation con-sumed as fuel averaged 5.5 per cent of pore volume. The effect of air pressure was, found to be .small for experiments having high combustion eficiencies. This study should promote a better understanding of the problems and mechanisms involved in labora-tory investigations and field applications of the in situ combustion pro-cess. The data presented will be use- ful in the interpretation of results of field tests. When tempered with volu-metric sweep efficiencies, the data can be used in making preliminary economic appraisals of the process as applied to reservoirs containing high porosity unconsolidated media. INTRODUCTION The purpose of this work was to obtain laboratory data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. In situ combustion basically consists of (1) injecting air into a reservoir through selected input wells to create an air sweep through the reservoir, (2) igniting the crude at the injection well, and (3) propagating the combustion front through the reservoir by continued air injection. By this means, oil is swept toward producing wells in the area. The fuel for combustion is supplied by heavy residual material (coke) which has been deposited on the sand grains during distillation and cracking of the crude oil ahead of the combustion front. Recovery of petroleum by a combustion or heat wave process is not a new idea. F. A. Howard was granted a patent in 1923 on a process in which air and a combustible gas were pumped into an injection well and ignited.' Russian engineers reported on field experiments with a crude oil gasification process in 1935'. Other known early field tests include those conducted near Bar-tlesville and Ardmore, Okla., in 1942." More recently completed field tests include an inverted seven-spot by Sinclair Oil Co. in the Delaware-Childers field, Nowata County, Okla.'; a three-well and an inverted five-spot test by Magnolia Petroleum Co. in Jefferson County, Okla."."; and a test by California Research Corp. in the Irvine-Furnace field in Kentucky. The Worthington Corp. has completed a test in cooperation with the Forest Oil Corp. in Clark County, 111.l Several field tests are now in progress. Sinclair has acquired a 600-acre lease in the Humboldt-Chanute field, Allen County, Kans., and is under way with a large-scale operation. Three field tests are under way in California. The General Petroleum Corp. is conducting an inverted five-spot pattern test in the South Bel-ridge field in Kern County under a cooperative agreement with 11 other companies, including Continental Oil Co. California Research Corp. is conducting a four-well pattern test in Midway-Sunset field near Maricopa, and Richfield Oil Corp. is under way with a test in the Ojai field in Ventura County. Although the published information is valuable concerning results of field tests, little laboratory data other than that reported by Kuhn and Koch5 are available to aid in appraising the tests from a technical or economic standpoint. Engineering data needed to evaluate the process include the amount of air required per barrel of oil recovered, minimum injection rates which will support combustion, rates of advance, air required per unit volume of reservoir cleaned, amount of oil recovered, and amount of oil consumed as fuel. The present laboratory investigation was undertaken to provide these data for that portion of the reservoir swept by the combustion zone. The first phase of this investigation was exploratory in nature and was conducted at injection pressures less than 100 psig. Data were ob-

Henry Louis, Newcastle-upon-Tyne, England (communication to the Secretary): I think very highly of the novel and ingenious device of Prof. Richards for analyzing the movement of the various elements of the jig; it is a method that certainly seems to promise valuable results, if we could only make certain that these various indicator-appliances have no effect upon the action of the jig. I would like, however, to suggest that in future experiments the connection between the plunger indicator-rod and the pencil should be made by means of parallel motions, so as better to reproduce the rectilinear motion of the piston. I should expect, if this were done, that the " curve " of the plunger in the Harz jig, at any rate, would be represented either by straight lines or else by quite regular curves, according to the method by which the plunger is set in motion; the apparent combinatioil of straight line and curve seems difficult to explain. With respect to the water-curve, I am afraid I am completely at fault, but no doubt Prof. Richards can explain my difficulty. In Fig. 2, the areas of the screen-side and the plunger-side of the jig are equal. If the piston be a fair fit and the bottom of

Jan 1, 1897

By Molly Gleiser, John Chipman

The standard free energy of formation of WC was obtained from determination of the equilibrium WC + CO2 = W + 2CO between 1215° and 1266°K. Its uallie is -8340 * 300 cal Per mole over the above range of temperature. AS a part of a program devoted to measuring the stabilities of the carbides, a study was made of the free energy of formation of tungsten carbide, WC. The homogeneity range of this compound is very small,' and it is generally accepted and is dealt with here as a stoichiometric compound. The heat of formation, ?H°f, of WC has been accurately measured by Huff, Squitieri, and snyder.2 The only attempt, however, to measure the free energy of formation of this compound was made by Schenck, Kurzen, and wesselkock3 who brought tungsten carbides into equilibrium with H2 and CH4. Unfortunately their results are not sufficiently accurate nor consistent enough to permit the calculation of free energies. METHOD Heating mixtures of tungsten and carbon powders in hydrogen for 4 days at 1050°C led to formation of some WC without any trace of W2C. It was deduced, therefore, that at least below this temperature W2C will not be formed during experiments with mixtures of tungsten and WC. This was subsequently shown to be correct. The method chosen was the measurement of the equilibrium of the reaction

Jan 1, 1962

By E. R. Gilbert

Klopp et al. have reported data on tensile and creep properties of are-melted and electron-beam-melted tungsten. We would like to point out some similarities between their creep results and ours on are-melted and powder-metallurgy tungstenand offer some alternate interpretations of the data which lead to different rate-controlling mechanisms. Klopp et al. observed extensive transient creep in the 2250" to 3500°F temperature range where the acthetivation energy is 106,400 ± 3300 cal mole-1. They suggest cross slip as the possible rate-controlling mechanism since "cross slip may occur only by the movement of screw dislocations, and not edge dislocations, thus allowing only partial recovery of the strain hardening and resulting in a continuously decreasing creep rate, characteristic of transient creep.'' Our tests on are-melted tungsten and powder-metallurgy tungsten displayed an extensive transient creep stage in the same temperature range but they also displayed a steady-state creep stage. The stress levels and strain rates of the two investigations, 1.4 to 7 kg mm-2 and 10-7 to 10-4 sec-1 for that of Klopp et al. and 4.5 to 10 kg mm-2 and 10-8 to 10-4 sec-1 for those of Gilbert et al., are overlapping. The activation energy for creep of our powder-metallurgy tungsten is 105,000 cal mole-1. This close agreement with the value found by Klopp et al. suggests that the same mechanism may be common to both types of materials. It may be possible to gain some additional insight into the rate-controlling mechanism by applying the analysis made by conrad22 in terms of the activation volume. The value for the activation volume depends upon the dislocation mechanism and may be used to help differentiate between various dislocation mechanisms. The activation volume for cross slip is 10 to 100 b3. Values determined from our data were 130 to 220 b3 which are in better agreement with the range of 102 to 104 b3 for nonconservative motion of jogs. Values determined from data of Klopp et al. are 240 to 1040 b3. We suggest that the rate-controlling mechanism for creep in this temperature range may be nonconservative motion of jogs assisted by enhanced diffusion along grain boundaries or dislocations. This model requires an activation energy lower than that for self-diffusion as is observed. If this is the controlling mechanism, a higher activation energy which is closer to that for self-diffusion might be expected for tests conducted on specimens with reduced grain boundary area, i.e., larger grain size. In support of this premise we have conducted tests on speci- mens having one to three grains per cross section for which a higher activation energy of 130,000 cal mole-1 was observed. Also, in agreement with results of Klopp et al., a faster creep rate resulted from the increased grain size and probable decreased dislocation density. Further argument against the cross slip mechanism is based on the constant activation energy we obsserved over the range of 5.0 to 10 kg mm-2,21 whereas the activation energy for cross slip displays a significant stress dependence.23 In addition to this, the powe on the stress term for the strain-rate dependence appears too high for cross slip. The values for tungsten fall in the range of 4.5 to 7 (Klopp et al. and Ref. 21) whereas values of approximately 2 are observed in creep by cross slip for hep metals.24 At temperatures from 3300° to 4000°F, Klopp et al. observed an activation energy of 141,000 ± 4000 cal mole-' which is less than that for self-diffusion, 153,000 cal mole-1, 25 and less than that reported for high-temperature creep of powder-metallurgy tungsten by Green:' 160,000 cal mole-1. Klopp et al. suggested that recovery of strain hardening by dislocation climb is the rate-controlling mechanism in this temperature region. Actually an activation energy larger than that for self-diffusion is predicted by this model if the temperature dependence of the elastic modulus27 is taken into consideration. Klopp et al. attributed this lack of correlation to the compositional differences between powder-metallurgy tungsten used by Green and their own arc- and EB-melted tungsten. It is our position that the value of 141,000 ± 4000 cal mole-' represents a transitional value between the higher and lower activation energies and does not represent a discrete mechanism of deformation. If the tests had been extended to higher temperatures the higher value of activation energy would have been observed as has been demonstrated by both our analy sis'' of isothermal test data by GE-NMPO28 and differential temperature tests28 on are-melted tungsten. The activation energies determined (170,000 and 160,000 cal mole-1) were greater than that for self-diffusion and are in better agreement with the value found by Green. The model of dislocation climb is associated with ; activation volume of 1 b3 according to Conrad.22 The activation volume calculated for the creep data of fou independent investigators in the temperature range where the activation energy for creep is near that for self-diffusion (Klopp et al. and Refs. 26, 28, and 30) is 110 to 2800 b3 and is in the range suggested for nonconservative motion of jogs. In the case of tungsten this mechanism may be preferred over that of dislocation climb. Sincere appreciation is expressed to Messrs. J. E. Flinn and F. L. Yaggee for the helpful discussions and suggestions in the preparation of this communication.

Jan 1, 1967

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

In the Ti-Cd system two intermediate phases, TiCd and Ti Cd, have been found and characterized by X-ray diffraction powder techniques. An earlier reference' had reported the existence of the compound Tisd. No structural details, however, were given nor was there any indication of the possible existence of other binary compounds. Studies of the solubility of titanium in liquid cadmium2 led to the discovery of both TiCd and Tisd. The solid phase in equilibrium with saturated solutions of titanium in liquid cadmium at temperatures below 620°C is TiCd, whereas TizCd is the equilibrium solid phase above 620°C. Both thermal analysis and X-ray studies show that a peritectic reaction between the y phase (~isd) and cadmium to form the 6 phase (Ti Cd) occurs at 620°C. X-ray diffraction powder photographs of material isolated from the ingots used in the solubility measurements as well as material prepared by a direct heat of the appropriate stoichiometric amounts of titanium and cadmium can be indexed on the basis of a tetragonal unit cell with a = 2.904 ± 0.002A, co = 8.954 * 0.004A, c/a = 3.083. No variation of lattice parameters indicative of a range of composition is evident. With four atoms in the unit cell the calculated density of the intermetallic is 7.05 g per cm3; the observed value is 7.07 g per cm3. The TiCd lattice is primitive as indicated by the fact that there are no systematic absences among hkl reflections. The absence of all hko reflections for which h + k = 2n + 1 is also evident. This systematic absence indicates the following two space groups, C\h — P4/n and D&~4/nmm; both groups, however, have the same two- and four-fold positions. Stoichiometry, symmetry and space group indicate two likely structure types. They are the PbO-litharge3 (B10) type and the Ti CU (B11) type. Spatial considerations favor the B11 structure with atoms placed in the following positions: 2Ti (c) 0, 1/2, Z; l/2, 0, Z 2Cd(c) 0, 1/2, Z; 1/2, 0, Z The TiCd structure may be summarily described as a layered structure in which double cadmium layers alternate with double titanium layers along the c-axis. The best agreement between calculated and observed intensities is obtained for the values ZTi = 0.608 and ZCd = 0.130. Calculated and observed powder intensities as well as other pertinent powder data are recorded in Table I. Interatomic distances for the proposed structure are recorded in Table II and are to be compared with the distances of closest approach for titanium and cad-

Jan 1, 1962

By Glenn A. Marsh, George Bernard

It is often assumed that aerated oil field brines which are to be injected underground contain dissolved oxygen in amounts which will cause appreciable corrosion. Through the use of a new portable dissolved oxygen meter, accurate determinations were made at three brine conditioning plants. At two older plants, dissolved oxygen concentration in the final treated brine was found to he almost zero In spite of aeration during the conditioning process. At a new plant, dissolved oxygen was initially present but disappeared soon after the brine was "inoculated" with oxygen-free brine from one of the other plants. Corrosion tests at the two older plants have substantiated predictions that the brines would lint be corrosive. These results show that mechanical deaeration may not always be required in brine treating plants. INTRODUCTION The present work was undertaken to add to our knowledge of aeration and deaeration of oil field brines in brine conditioning plants. It is commonly assumed that brines which are exposed to the air soon become more or less saturated with dissolved oxygen. Since oxygen-containing brines are known to be corrosive, precautions are often taken to keep air out of brine through the use of closed systems or mechanical deaeration. The study of oxygen in brine has been seriously hampered in the past because of the lack of a suitable analytical tool. The standard Winkler method for the determination of dis-solved oxygen is satisfactory for use in fresh water, but not in many oil field brines. Corrections have to be made for a number of reducing substances such as ferrous iron and hydrogen sulfide which are commonly present in natural brines. Very often the correction factors are much greater in magnitude than the amounts of oxygen which are to be determined, and consequently erroneous results are obtained. Also. erratic Winkler data are obtained when appreciable concentrations of calcium and magnesium salts are present. The first step in carrying out a systematic study involved designing a portable dissolved oxygen apparatus which would operate in natural brines. Subsequently, this apparatus was used in three brine conditioning plants. Dissolved oxygen data obtained here, and certain corrosion rate data, illustrate the interesting behavior of oxygen in these oil field brines. APPARATUS A portable dissolved oxygen meter described in detail elsewhere,' was developed specifically for use with oil field brines. It is a polarographic apparatus employing a small rotating platinum electrode (cathode) and calomel reference electrode (anode). A potential of 0.7 volts is applied across the electrodes while they are immersed in the brine to be tested. 4References given at end of paper.

Jan 1, 1952

By C. T. Holland

This discussion is concerned with those com-J- paratively infrequent bumps that eject material from the failed mass with enough energy to wreck heavy machinery and seriously injure or kill people. In such cases there is a loud report, and the pressure waves set up in the mine atmosphere wreck ventilation controls several hundred feet from the site of the failure. Vibrations are induced in the earth's crust which may be detected several miles from the point of origin, and explosive gases may be released in large quantities." Usually a dense suspension of dust is produced from the failed mass, together with dust placed in suspension by the resulting air blast. These rock bursts or bumps have also been called mountain shots, bounces, pillar bursts, and crumps. Such occurrences, when extensive, are serious catastrophes, and may force abandonment of the mine.' CAUSES OF ROCK BURSTS Rock bursts in coal mines have occurred in sev-eral places under diverse geological conditions, mining methods, and/or practices. A study of many such occurrences indicates that they depend on the following conditions: 1) cover thickness of 500 ft or more, 2) cover composed of strong members and having a strong member lying close to or on the coal bed, and 3) a floor that does not readily heave. The minimum thickness of cover under which coal mine rock bursts occur is based on observation. Under unusual circumstances involving very strong roof members and/or mining systems, and/or practices especially likely to induce bursts, a burst conceivably could occur under less roof. Under special circumstances rock bursts have occurred in marble quarries almost at the surface.' Furthermore, under very heavy cover it is likely that controlling roof members need not be as strong and as close to the coal bed to cause bumps. Just what constitutes a strong roof or roof member is open to question. Obviously the strength of a roof member is determined by its thickness, the distance between bedding planes across which little or no bond exists, the spacing and development of joints, and the inherent strength of the rock material. Strata sections showing roofs under which rock bursts in coal mines have developed are illustrated in Fig. 2. In several instances the strength of rocks composing the roof of mines developing bumps has been tested. The tests (Table I) show that these rocks develop considerable strength in compression, bending, and shear and that in some cases the strengths are very high. No quantitative data are available concerning joints in roof members over coal beds where rock bursts have occurred, but the author has examined many mines subject to bursts and has received the impression that joints in the shales immediately over the coal beds are always present and well developed. In the main sandstone or conglomerate members themselves, however, where observed, he has yet to see a fracture system indicating well developed joints. Undoubtedly joints are present, but the evidence indicates that they are few, poorly developed, and widely spaced. In a mine subject to bumps, moreover, actual measurements of roof spans up to 225 ft between supports under a cover of about 800 ft have been made before roof failure occurred. Such spans signify strong roof. In coal beds subject to rock bursts, the bottom rock is usually a sandy shale. A few tests (Table I) have been made on the floor rock of coal beds. Observations in mines indicate that they are usually weaker than roof rocks and that under load they show more plastic effects. Observation in ground subject to bursts invariably indicates a relatively strong floor highly resistant to heaving, although some heaving may occur. Other factors listed as favorable to rock bursts are: 1) mountainous surface; 2) steeply dipping beds; 3) proximity of faults, folds, and other similar geologic structures. Many bursts have occurred in mines under mountainous country, although many bursts in mines under a surface with little relief indicate that thickness of cover, not relief, is the essential factor. In steeply dipping beds, many bursts occur in mines that are essentially flat, and rock bursts have been recorded in beds dipping as much as 35o Most rock bursts in the U. S. occur in beds that dip less than 10 pct. It is also true that most U. S. coal is produced from beds dipping less than 10 pct. Geologically, faults are regarded as providing stress relief, but in the vicinity of faults, as well as sharp folds, it would seem that residual stresses could be present. The fact that rock bursts occur in areas remote from faults and sharp folds suggests that their presence is not necessary for this phenomenon to take place. There have been many bursts close to faults and folds, and it may be assumed that occasionally such structures accentuate their occurrence3 The conditions and circumstances under which they occur, coupled with the effects produced, leave In the Crowsnest Pass coalfield, British Columbia, a rock burst is estimated to have released 1.8 million cu ft of methane.

Jan 1, 1959