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By John Wulff, J. H. Hollomon

Service failures in brass condenser tubes are often due to corrosion. One of the commonest types of corrosion reveals a surface structure of redeposited copper.' The study of the effect of alloy addition agents in preventing this kind of corrosion has received impetus from the extensive publication of Bengough and May.2 The mechanism of such inhibition gauged from immersion corrosion,2 cell corrosion,3 and electrolytic potential4 measurements is controversial. This controversy may be attributed in part to a lack of definite knowledge5 of the actual nature of the initial films formed in corrosion experiments. In our own corrosion work on copper and 70-30 brass this lack became apparent and necessitated an examination of surface films by X-ray and electron diffraction methods. The present paper is but an introduction to the subject of inhibition and reports the structure of films formed in active corrodents. Experimental Procedure The arsenical coppers and brasses used in this investigation were made by one of the writers* in the plant of the Revere Copper and Brass Co. at Rome, N. Y. Standard commercial melting practice was followed. O.F.H.C. copper and electrolytic zinc were used and all arsenic additions were made by additions of a master copper alloy. The final analyses are given in Table I. Likewise, the extrusion, cold-rolling, and intermediate anneals employed followed standard usage. Final heat-treatments were given to all materials to produce a similar grain size (0.035 to 0.045 mm. for brass and 0.015 to 0.025 for copper) for the alloys containing various percentages of arsenic. Samples 1/2 by M by 1/4 in. were cut from sheet material resurfaced and finished with 0000 metal-lographic papers. The surfaces were all degreased in alcohol and benzine before immersion. After immersion in the corrodent, they were washed gently in tap water, dipped first in alcohol and then in pure benzine and allowed to dry in the diffraction apparatus. The reflection electron diffraction apparatus used has been described by Burwell and Wu1ff.6 Fig. I is typical of the photo-grams obtained. The X-ray apparatus was

Jan 1, 1941

By John Wulff, J. H. Hollomon

Service failures in brass condenser tubes are often due to corrosion. One of the commonest types of corrosion reveals a surface structure of redeposited copper.' The study of the effect of alloy addition agents in preventing this kind of corrosion has received impetus from the extensive publication of Bengough and May.2 The mechanism of such inhibition gauged from immersion corrosion,2 cell corrosion,3 and electrolytic potential4 measurements is controversial. This controversy may be attributed in part to a lack of definite knowledge5 of the actual nature of the initial films formed in corrosion experiments. In our own corrosion work on copper and 70-30 brass this lack became apparent and necessitated an examination of surface films by X-ray and electron diffraction methods. The present paper is but an introduction to the subject of inhibition and reports the structure of films formed in active corrodents. Experimental Procedure The arsenical coppers and brasses used in this investigation were made by one of the writers* in the plant of the Revere Copper and Brass Co. at Rome, N. Y. Standard commercial melting practice was followed. O.F.H.C. copper and electrolytic zinc were used and all arsenic additions were made by additions of a master copper alloy. The final analyses are given in Table I. Likewise, the extrusion, cold-rolling, and intermediate anneals employed followed standard usage. Final heat-treatments were given to all materials to produce a similar grain size (0.035 to 0.045 mm. for brass and 0.015 to 0.025 for copper) for the alloys containing various percentages of arsenic. Samples 1/2 by M by 1/4 in. were cut from sheet material resurfaced and finished with 0000 metal-lographic papers. The surfaces were all degreased in alcohol and benzine before immersion. After immersion in the corrodent, they were washed gently in tap water, dipped first in alcohol and then in pure benzine and allowed to dry in the diffraction apparatus. The reflection electron diffraction apparatus used has been described by Burwell and Wu1ff.6 Fig. I is typical of the photo-grams obtained. The X-ray apparatus was

Jan 1, 1941

GEORGE K. BURGESS,* Washington, D. C. (written discussiont).-Professor Sauveur refers to the International Aircraft Standards Board in terns that would indicate his non-familiarity with, the organization and the working of this Board which, of course, is excusable on account of Professor Sauveur's absence in Europe at the time. He implies .that the work of this Board was entirely dominated by American interests, whereas diametrically the opposite was the case. The Board, was organized for the purpose of facilitating purchase in the United States, on the basis of common specifications, by the Allied air, services in the United States, and the Board performed a very valuable service in unify-ing the specifications of Italy, Great Britain, France, Canada, and the United States for such purposes. The proceedings of the Board were car-ried out on the basis of unanimous agreement of the representatives of the five countries and all the members from each of the countries were technical specialists or, had the advice of technical assistants. It would be difficult to find an instance of greater unity of purpose, readiness to' compromise, and efficient production than was shown by this Board, which produced seventy-eight specifications, in the preparation of which representative American manufacturers appeared before the Board.

Jan 12, 1919

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 Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By I. N. Knapp

I Herewith present some notes on the use of Portland cement to cement in the casing, and for plugging, to exclude water from oil and gas wells, and the methods employed. I have used my best efforts to. make each step of the operation of cementing wells perfectly clear. The information is the result of actual experience and observation. The illustrations are from original drawings made especially for this paper. Portland Cement It is not necessary to discuss here the manufacture of cement. Any established brand of the slower setting Portland cements may be purchased with the confidence that it will harden, if properly used, and exclude water from and plug wells efficiently. Setting.—By the setting of cement is meant its initial change from a soft or plastic mortar to a friable solid. After the cement has become thoroughly set it is still very weak and can be readily pulverized in the fingers. Setting is thought to be effected by the crystallizing out of the silicate and the aluminate of lime, which are soluble in water in their anhydrous form. After dissolving in the water they pass to the hydrated state, in which they are insoluble, and hence are precipitated in a crystalline form. Ordinarily neat Portland cement mortar remains perfectly plastic for from 1 to 1 1/2 hr. after mixing with water at about 70" F. A higher temperature accelerates and a lower retards setting.. Hardening.—This is due to a continual crystallization of salts from solution, and to further chemical and physical changes which develop slowly, but which continue for long periods of time. Testing.—It is no more necessary for an operator to go into the scientific testing of cement to be used in a well than to so test the pipe used. He must depend for the quality of each on the tests and reliability of the manufacturer. Cement or pipe may be damaged in shipment so

Jan 1, 1915

By C. P. PERIN, DONALD BELCHER

T HE production of pure iron by electrolyzing solutions of its salts has been the object of scientific curiosity and research for about 80 years; and in the last two decades a realization of the unusual physical and chemical qualities of electrolytic iron has turned the attention of chemists and metallurgists toward a commercial application of this accumulated knowledge. Thus Burgess and Hambuechen in America, . Cowper-Coles in England, and Fischer in Germany- devised methods, more or less successful, for the electrolytic refining of iron, but none of these processes has yet attained large-scale operation. During the war some interesting ,work was done in France and England on building up worn or defective machine parts by electrodeposition of iron. It remained for the Société "Le Fern in France to carry on the process commercially. For six years Les Fonderies et Forges. de Sainte-Maire et Gravigny and the works of Bouchayer & Viallet at Grenoble have manufactured pure-iron boiler tubes in competition with established practice. The French process originated in the researches of Anthelme Boucher in 1910, and was, not put into operation until several years of experimentation had passed.

Jan 1, 1921

By W. G. Frailing, W. P. Sims

The Lakeview Pool of Kern County, California, was discovered in 1910 with the drilling of Lakeview No. 1 which blew out and produced an estimated 8,250,000 bbl of oil in 544 days of uncontrolled flow. The well has since been known as the Lakeview Gusher. Full exploitation of the pool did not take place until about 25 years later. A total of 112 producing wells were completed in the Lakeview sand through April 30, 1949. As of that date, about 30 per cent of the total wells drilled were still producing, with an average pool production rate of approximately 2000 bbl per day. The cumulative oil production was about 41 million bbl of oil, or 55.3 per cent of the tank oil originally in place. The pool is bordered on its down-structure side by a body of inactive edgewater and water production where present has been principally the result of coning. Since the depletion of the greater portion of the gas energy by the Lake-view Gusher, the pool has operated under gravity drive. Relatively high angle dips, good permeabilities and favorable fluid characteristics have made gravity drainage particularly effective. Since January, 1942, the oil recovery -has been relatively constant at about 53,000 bbl per ft drop in fluid level. Correlations between the volume of reservoir space drained and the cumulative oil produced indicate that an ultimate recovery of 63.3 per cent of the tank oil originally in place is attainable. INTRODUCTION The Lakeview Pool is an outstanding example of gravity drainage. It is one of many productive reservoirs of the Midway-Sunset Field, and is located in Kern County, approximately five miles southeast of Taft and two miles north of Maricopa, California. Its position rel- ative to surrounding pools and to the Thirty-Five anticline is shown on Fig. 1. The northern portion of the pool lies in sections 32 and 33, Township 32 South, Range 24 East, Mt. Diablo Base and Meridian, while the southern portion lies in sections 25, 26, 35 and 36, Township 12 North, Range 24 West, San Bernardino Base and Meridian. As no two sections bear the same number, they will hereafter be referred to by section number alone. The purpose of this paper is to review the performance of the Lakeview Pool in an effort to evaluate the effectiveness of gravity drive as a recovery mechanism. REGIONAL STRATIGRAPHY AND STRUCTURE The oustanding structural feature is this area is the Thirty-Five anticline, the axis of which plunges South 75" East through the center of Section 35. As shown on Fig. 2, the following zones are oil and gas bearing in the Thirty-Five anticline area: Pleistocene Basal Tulare Tar Sands Pliocene San Joaquin Mya Sands Top Oil or Scalez Zone Etchegoin Kinsey Sand Wilhelm Zone Gusher Sand Calitroleum Sand Miocene Reef Ridge Lakeview Sand Sub-Lakeview Miocene Sands Monarch Sands or fractured shale equivalent Maricopa Webster Sand or fractured shale equivalent Fractured Shale-Uvigerina Zone C Obispo Sand and fractured shale equivalent Pacific Shale Zone The productive interval of the Lakeview Pool is limited to Upper Miocene and Lower Pliocene deposition. In this general area, the most prevalent type of accumulation results from stratigraphic traps or permeability pinchouts. As is the case of the Lakeview Pool, strati-graphic traps resulting from angular unconformities are present. The structure within the Miocene does not parallel that of the Etchegoin (Pliocene), as the Miocene beds were folded, and in places faulted, and subjected to erosion prior to Pliocene deposition. The Lakeview horizon consists of truncated sands which occur on the northeast flank of the Thirty-Five anticline. The direction of strike is west and northwesterly through sections 25 and 36 and continues northwesterly through sections 26 and 33, to the approximate center of section 32. At this point the strike swings to the northeast and the horizon re-enters section 33. in the northwest corner. The change in strike in section 32 affords synclinal accumulation at that point. The Lake-view sand is truncated updip by the Etchegoin overlap. To the southeast, the sand shales out, while to the northwest, the productive interval appears to be limited by a combination of stratigraphic pinchout and permeability barrier. Structurally, the Lakeview reservoir presents three areas of interest, as shown on Fig. 3. Area I in section 32 is a region in which a productive Sub-Lakeview Miocene sand is present. It occurs from 10 feet to 30 feet below the base of the Lakeview sand and attains a maximum thickness of 25 feet in Well No. 21, section 32. The producing characteristics of the Sub-Lakeview Miocene sand differ radically from those of the Lakeview sand. Water production at high structural locations and abnormally high fluid levels indicate that there was no communication with the Lakeview sand. Wells in Area I penetrated this sand and produced it in conjunction with the Lakeview sand. In Area 11, the Lakeview sand is a

Jan 1, 1950

By Richard Miller

RECENT studies of creep have made it apparent that plastic deforma-tion may occur in metals under stresses less than the elastic limit as deter-mined from short-time tests. In summarizing conclusions drawn from creep tests by various investigators, Tapsell1 said: "It is evident that if a material has a true elastic range, the elastic limit must represent the maximum stress for no creep." The presence of a. definite elastic limit, represented in single crystals by a critical or threshold shearing stress, is claimed by Schmid2, Elam3 and others who have investigated the plastic deformation of single crystals. However, this "law of critical shearing stress" was deter-mined2 from short-time tests, and the measurement of the deformation was made with apparatus primarily designed to observe large amounts of plastic deformation, not to detect elastic changes. Experimental data recently obtained with highly sensitive instru-ments by A. W. Hanson4 on zinc and by Podaschowsky5 on rock salt indicate that the elastic range in single crystals is considerably narrower than formerly was supposed. Moreover, a theoretical possibility of permanent deformation, under the influence of even the smallest shear stress in single crystals above a certain temperature (Td), has been developed by G. I. Taylor6. This evidence seemed to warrant an examination of the elastic limit in large single crystals by means of creep tests. The first metal chosen for examination was zinc.

Jan 1, 1936

By Anders Carlson

NOTABLE advances have been made in the evaluation of oil-reservoir rocks from information furnished by core analysis. Among the physical data employed, per-meability is of primary importance. It may be assumed that the permeability of a core sample, considered as a property inherent to the nature of the porous medium only, is not markedly altered by the coring opera-tion, therefore some degree of accuracy is justified in the laboratory determination of permeability constants by means of homo-geneous flow media. To provide that such relatively simple determinations be sus-ceptible to duplication and consistent inter-pretation should prove advantageous in the prediction of subsurface flow conditions involving nonhomogeneous fluids. The air permeameter seems to fill most satisfactorily the need for rapid and fairly accurate determinations. Instruments that are similar in design and operation have come into general use. However, this has not resulted in an encouraging uniformity in the results obtained. Recognizing the value of reducing measured values to a common quantitative standard, the authors have sought to determine possible reasons for undue discrepancies and means for their elimination. This paper will be specifically concerned with three factors, which appear to be of some importance in the establishment of consistent permeability values: (I) design and operation of the permeameter, (2) preparation and mounting of the sample, (3) type of flow created in the sample.

Jan 1, 1940

By Kent R. Van Horn, W. P. Sykes

Since Honda and Murakamil in 1918 proposed their constitutional diagram of the carbon-free iron-tungsten system, considerable effort has been expended by several investigators in attempts to define more positively the structural features of the alloys. The existence of an intermediate phase corresponding to the formula Fe3W2 (68.7 per cent W) was proposed from evidence of a purely metallographic nature by one of the present authors2 in 1926. Since that time the identity of this phase has been confirmed by Arnfelt3 and by Takeda,4 both of whom employed X-ray methods as well as the microscope and the chemical analysis of isolated microconstituents. According to Arnfelt, Fe3W2, as crystallized from the iron-rich melts at a temperature above 1450° C., contains by analysis 68.7 per cent W. The lattice of this phase is characterized by trigonal symmetry. Arnfelt, moreover, proposed a second intermediate phase formed at some temperature between 1450" and 1000" C. by a peritectoid reaction involving Fe3W2 and the iron-rich solid solution. A melt containing 25 per cent W was cooled to 1000" C. and heated for 100 hr. The precipitated tungsten-rich constituent was separated and found by analysis to contain 62.6 per cent W. This composition agrees closely with that represented by the formula Fe2W (62.2 per cent W). Diffraction patterns from the concentrated precipitate showed a hexagonal unit cell. Takeda confirmed the data of Arnfelt regarding Fe3W2 but was unable to detect Arnfelt's second intermediate phase. While Takeda failed to describe in detail the treatments employed, he stated that in alloys containing 40 per cent W which were quenched after heating at various temperatures between 1200" and 1450" C. no evidence of the second phase (Fe2W) was observed 'either in the microstructure or in the diffraction patterns of isolated residues. He therefore considered the existence of this low-temperature hexagonal compound as disproved.

Jan 1, 1933

By L. D. Wooddy, Robert Moscrip

The simultaneous solution of the volumerric balance and the unsteady-state equation has been used for several years to make performance calculations for combination drive reservoirs. This method makes possible the calculation of volumetric changes of fluids in the gas cap, oil zone, and aquifer which occur as a result of withdrawals and reservoir pressure changes. It does not provide a means for the determination of reservoir fluid distribution changes corresponding to these vollrmetric changes. A knowledge of the fluid saturation distribution in the reservoir at various stages of depletion is important for the determination of the efficiency of gas and water as oil-displacement media and, therefore, for the reliable predicrion of ultimate oil recovery. To provide this knowledge, the displacement equations are solved simultaneously with the volumetric balance and unsteady-state equations. The described calculation procedure has been used satisfactorily to analyze the past performance and to predict the future behavior of combination drive reservoirs under both primary and pressure-maintenance operations. INTRODUCTION The three basic mechanisms by which oil is displaced from a reservoir are: (1) dissolved gas drive—the displacement of oil by the expansion of liberated solution gas, (2) water drive—the displacement of oil by water which enters the oil zone from the aquifer, and (3) gas cap drive—the displacement of oil by gas which ex- pands into the oil zone from the gas cap. The action of gravitational forces may be effective in increasing the efficiency of the basic drive mechanisms. Gravitational forces favor the segregation both of gas and oil and of oil and water, thus tending to shorten the transition zone between oil and displacing fluids. Most reservoirs produce under the influence of a combination of these drives and are designated "combination drive reservoirs". Fig. 1 is a cross section of a typical combination drive reservoir. A calculation procedure for analyzing the performance of combination drive reservoirs has been developed by combining the displacement equations' with the volumetric balance equation' and the unsteady-state equations. The pressure-production performance and the positions of the gas-oil and oil-water contacts are calculated for several stages of reservoir depletion by solving these equations simultaneously, thus affording a basis for: 1. Determining instantaneous and ultimate oil, gas, and water production under various operating conditions. 2. 'Establishing a maximum efficient rate of production, 3. Determining the advantages of pressure maintenance and unitization, and 4. Designing surface installations necessary for primarv and pressure-maintenance operations. DEFINITIONS The calculation procedure for combination drive res-

Jan 1, 1957

By Ralph M. Hunter

UNTIL recent years, maintenance of surface coal handling facilities was a relatively simple task. Equipment consisted principally of conveyors, screens and crushers of comparatively simple construction. Electrical equipment consisted of motors and starters, with little, if any, interlocking. In most cases failure of any component affected only the grades of coal loaded so that even a prolonged break-down did not affect mine operation materially. However, with the introduction of modern cleaning plants, the picture has changed. The equipment is much more complex and therefore more difficult to maintain. In many cases failure of any component of the plant prevents loading of coal. Even if provision is made to by-pass, the quality of coal loaded is lowered, affecting markets. In the case of plants designed to permit full seam mining, marketable coal cannot be loaded without operation of the cleaning plant. Under these conditions it is apparent that considerable thought and effort toward better maintenance are justified. In order to assure continuous, efficient and economical operation, maintenance should receive consideration, not only after the plant is in operation, but while it is being designed. It is hardly necessary to say that the designer should strive for sturdiness and wearing qualities. It is sometimes not realized, however, that even the best parts will sooner or later require replacement or repair. The designer should, therefore, give consideration to accessibility. Anyone who has had to do with cleaning plant maintenance is familiar with installations where several hours are required to get at a part that can be repaired or replaced in a few minutes, once it is accessible. As in most cases, experience is the best guide. The men who operate and maintain this equipment know the problems encountered. Whenever available, the opinions of these men should be sought and heeded. As an example, we might consider the refuse elevator on a Chance Cone. Our company is now operating three of these cones, the first of which was installed in 1941, and the latest in 2946. Exact records are not available, but well over 50 pct of delays charged to the Chance Cones have been caused by the refuse elevator. This elevator receives refuse from the cone and carries it to a point above the water level of the cone, discharging onto a dewatering and desanding screen. Since the elevator operates under water and necessarily has close clearances in the lower boot, it tends to jam on large pieces of refuse or tramp iron. The chain, buckets and boot are also subjected to the action of water, sand and refuse, which accelerate normal wear. In case of jamming or chain-breakage it is necessary to drain the elevator and the cone so that even a minor fault in the elevator causes a considerable loss of time for the cone. In our new plant, which will contain two Chance Cones, the refuse elevator has been eliminated. This was accomplished by raising the cone so that the refuse gates could discharge directly onto the dewater-

Jan 1, 1948

By Allan D. Taylor

INTRODUCTION From the designer's view, the installation starts with the first definition of the orebody, and progresses through a long and complex development. The design is affected not only by the characteristics of the ore, but by all of the personalities and events of the project during its development. The following discussion attempts to touch on the most important aspects which define the context in which the designer must work in apply the do's and don'ts. That context is the basis of the viewpoint. WHAT CAN GO WRONG The Project Is Going Over Budget This is a common and serious concern to the plant designer. The Project Falls Behind Schedule Another common and disturbing condition with which the plant designer must cope. Some Equipment Fails to Perform This can be due to either faulty equipment or operating deficiencies. It can be the result of a wide variety of causes, but the designer will be an interested party in the search for the cause and the cure. The Plant Isn't Flexible Enough Sometimes a plant will handle some or even most of the ore satisfactorily but is unable to treat another type properly. This can be a significant problem. An example might be a case where low capacity of a cyclone feed pump makes it impossible to accompany an increase in grinding mill throughput with a corresponding increase in dilution water. This could lead to an increase in cyclone feed density, and a loss in product grade or a limit on the plant capacity. Spillage And Cleanup Are Excessive This is one of the most common and annoying defects in metallurgical plants, and one for which the designer can rarely delegate blame. Maintenance Is Excessive Another common complaint in new plants, and also one for which the dedesigner must accept most of the responsibility.

Jan 1, 1982

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By Joseph Hartshorne

The attention which this process has attracted, especially in Europe, has led me to believe that members of the Institute would be interested in a report of the progress which has been made in the year and a half that has elapsed since my paper on the subject was read at the Colorado Meeting of this Institute. As already described in that paper (Duns., xxvi., 380), this process is a modificatioii of the open-hearth steel manufacture, whether acid or basic, collsistillg essentially in the division of the charge between two furnaces, one of which is charged about two hours earlier than the other, and tapped into the other after the charge in the latter has become fluid, the slag of the first bath being removed from it during the transfer. This description still remains true as far as it goes, but further experience has demonstrated that circumstances will very materially modify the relation of the two furnaces to each other, and the character of the work done in each of them. The function of the primary furnace has become more clearly and entirely that of doing the rough work of desiliconiziug and dephosphorizing, while that of the second or finishing-furnace has become almost entirely that of decarburizing and finighing the heat. To indicate these developments and their results is the object of this paper. In order to avoid needless repetition, I shall try to accomplish part of this object by giving a short resume' of what has been published elsewhere on this subject since my former paper was read. This will at least enable those interested to study the matter for themselves from original sources. Since that time the following papers have been read and published: " The Bertrand-Thiel Process of Making Steel," by Percy C. Gilchrist (Cleveland Institution of Engineers, Session of 1896-

Jan 1, 1899

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By A. B. Kinzel

INCLUSIONS of nonmetallic matter have long been recognized as objectionable in steel. A complete theory of the effect of inclusions, which is consistent with that held today, was outlined in Howe's early work on the metallurgy of iron and steel. This, by analogy with wrought iron, assumes that the observed difference in properties between specimens with and across the direction of rolling is due to slag enclosures. The fact that wrought iron shatters in ballistic test is taken as an indica-tion of the effect of inclusions on the resistance to shock. Since that time, the development of the metallurgical microscope has shown the discrete nonmetallic inclusions in the iron matrix. Better resolution has, brought out the great number of inclusions, and the availability of good microscopes in steel mills and laboratories has constantly drawn more attention to these inclusions. This recent emphasis on inclusions has resulted in studies as to their nature, mode of formation and methods of elimination, such as the work of Wohrman, Dickenson, Herty, and Schenk. In addition to the published works; many investigations which have not been published' have been carried out by private laboratories and have resulted in the application of specifications intended to limit inclusions in many qualities of steel. Nevertheless, a clear understanding of the quantitative effect of inclusions on the physical properties of steel has been lacking. It is the specific purpose of this study to determine the quantitative effect of inclusions on the physical properties of steel that determine its behavior under dynamic stress. The study has shown that a quantitative relation between counted inclusions and impact strength does exist in normalized steels, but 'that factors other than readily visible inclusions are equally important. Furthermore, the present commercial rating of inclusions is unreliable with respect to counted inclusions or dynamic tests, and this study indicates that the tensile-impact test is more reliable as a measure of quality.

Jan 1, 1931

By AIME AIME

ANNOUNCEMENT on August 6 of the historic event of dropping an atomic bomb on Hiroshima, Japan, was more dramatic even than V-E day, since that had so long been forecast whereas the bomb production had been the best-kept secret of the war, even though at one time more than 100,000 people had been at work in connection with its production, and some two billion dollars had been spent on the project. Mining men had long been aware of an unexplained abnormal interest in uranium production, and suspected that something of the sort was on foot, while metallurgists were aware that various men of their acquaintance were engaged in some top secret research. The first announcement was soon supplemented by other official releases which told more about the research laboratories for theoretical and pilot studies, and the plants in Tennessee and Washington, but none of them made clear what the modus operandi is of these terrific bombs. Inquiry at Colum. bia University, where Dr. Dunning and his associates had succeeded in 1939 in splitting the uranium atom, and where laboratories known only as SAM have been feverishly active since the beginning of the war, was unproductive, since none of those officially connected with the project could give out anything beyond the official releases.

Jan 1, 1945

By J. B. Scott, J. L. Popham, H. F. Coffer, J. J. Reynolds

This paper concerns field experiments to define the areal extent, orientation and thickness of an artificial fracture in the Sacatosa field, Maverick County, Tex. The fracture was made by a sand-oil treatment of 176,-000 gal of lease crude containing a fluid-loss additive and 270,000 lb of 20-40 mesh subangular Poteet sand. The well was perforated with a jet gun, consisting of six shots in a single plane. Fourteen test holes were drilled at various locations around the fractured well. Drill-stem tests, Micro and Sonic Logs, coring and sampling of formation cuttings were used to determine the presence of the fracture in these holes. The test holes were drilled at distances up to 250 ft in a radial pattern around the fractured well. In addition to fracture areal extent and orientation, sand grain size before and after fracturing, erosion of perforations and fracture thickness were studied. INTRODUCTION The orientation,12 areal extent3, 4 and thickness5-9 of artificially induced fractures in reservoir rock by hydraulic means have been discussed in great detail in the oil industry in recent years. Methods for initiating vertical"' and horizontal" fractures have been tested in the laboratory and the field. Although the methods used give successful well stimulation, good field data on the physical characteristics of the fracture are lacking in the literature. It is recognized generally that properties of a fracture, such as thickness, sand placement in the fracture" and shape, may vary from reservoir to reservoir. This paper gives data on size, orientation and sand placement in a large fracture initiated in a single plane in Sacatosa field, Maverick County, Tex. It is not intended as a speculative study; rather, it is restricted to actual field data on fracture properties. No attempt is made to prove that the same type of fracture occurs in all wells. The field procedure was to drill 14 test holes at various locations around the fractured well. By employing several different testing techniques, the presence of the fracture and some of its characteristics were determined. These techniques as well as the results obtained are discussed in detail in this paper. DESCRIPTION OF FRACTURE TREATMENT N. J. Chittim Well No. 37-1, completed in the San Miguel No. 1 sand, Sacatosa field, Maverick County, Tex., was chosen for the field study. The San Miguel sand is a tight, well consolidated sandstone with an average porosity of 23 per cent. The permeability ranges from 0.1 to 10 md, with a median permeability of 2.3 md. The sand thickness averages 23 ft and is located at depths of 1,150 to 1,700 ft throughout the field.I3 The fracture treatment performed on Well 37-1 was as follows. 1. The well was drilled to a depth of 1,438 ft with native mud, and 51/2-in. casing was set and cemented to the surface. 2. The casing was perforated at 1,349 ft with a fracture-initiating jet gun. This gun consists of six shots, 7/16-in. diameter in a single horizontal plane. The jets were oriented in two groups of three, 180" opposed. The perforating device was designed to initiate a fracture perpendicular to the wellbore.