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By J. C. Reed, J. M. Hansell

Cinnabar was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigell by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done considerable exploration work and has retorted the high-grade ore so obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district. In March, 1934, the United States Geological Survey began a study of the Arkansas quicksilver district, which was made possible by an allotment of funds from the Public Works Administration. Until

Jan 1, 1935

Cinnabar was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigell by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done considerable exploration work and has retorted the high-grade ore so obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district. In March, 1934, the United States Geological Survey began a study of the Arkansas quicksilver district, which was made possible by an allotment of funds from the Public Works Administration. Until

Jan 1, 1935

By A. L. Blomfield, M. J. Trott

ThE Golden Cycle Mining and Reduction Co. operates its custom mill at Colorado Springs on Cripple Creek ores exclusively. These ores are straight sulfo-tellurides, with practically no base metals such as Pb, CU, Zn, As, or Sb. Upon entering the mill, the ore all passes through the sampler to storage bins, where beds of 5000 tons each are made to insure uniformity in roasting. Classification of ORes For efficiency, it has been found advisable to separate the ores into two classes according to their lime content. Other constituents have their effect, such as alumina and magnesia, but, speaking generally, these are roughly proportional to the lime, which, as CaO, is used as the indicator. Class A contains not more than 2 per cent. CaO and comprises about 66 per cent. of the ore treated. Class B contains over 2 per cent. CaO, and comprises 34 per cent. of the ore treated. Typical analyses of both classes are as follows: Class A a B Insol.......................... 86.70 75.90 Al2O3........................:.. 2.30 3.40 Fe.............................. 3.26 3.48 CaO............................. 1.57 5.12 S............................... 1.79 1.80 MgO........................... 0.21 1.08 Ignition loss..................... 3.20 6.50 99.03 97.28 The beds of each class of ore are made as large as possible with the available ore as it comes in, to avoid changing from one bed to the other any oftener than necessary. Each roaster will handle 50 per cent. more of class A ore than of class B, with practically the same results. This necessitates changing the rate of feed for each new bed and tends toward a poor roast and loss of tonnage at each change.

Jan 1, 1919

By J. C. Reed, J. M. Hansell

Cinnabar was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigell by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done considerable exploration work and has retorted the high-grade ore so obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district. In March, 1934, the United States Geological Survey began a study of the Arkansas quicksilver district, which was made possible by an allotment of funds from the Public Works Administration. Until

Jan 1, 1935

By Wheeler North

THE United Eastern Mining Co.'s property is located in the Oatman, Gold Roads mining district of Mohave County, Ariz. The mine and mill are some 26 mi. (41.8 km.) southwest of Kingman, the nearest railway connection. The ore consists of a mixture of calcite and quartz with some andesite. The values, which are mainly gold, alloyed with approximately 34 per cent., by weight, of silver, are extremely fine so that fine grinding is a most important factor in extraction. The milling process, briefly, consists of single-stage, coarse-crushing, two-stage ball milling in cyanide solution, followed by combined mechanical and air agitation, and by straight counter-current decantation. The Merrill zinc-dust precipitation method is used to recover the values, and is preceded by the Crowe vacuum treatment of the solution. The most notable features of the plant are the absence of filters, and the use of short peb mills loaded with steel balls, for fine grinding. As originally designed, the capacity of the mill was to be 200 tons per day, although the grinding end was to be capable of handling double that amount. By adding extra agitators and thickeners and by some alterations to the grinding end, the daily capacity has been raised to 285 tons. This, it is hoped, may be increased to 300 tons during the warm months of the present year. TONNAGE MILLED PER DAY 1917 average 234 Maximum month 272 Minimum month 146 1918 average 253 Maximum month 276 Minimum month 217 As this article primarily deals with plant operations, those interested in the mechanical description are referred to the article by Mr. Otto Wartenweiler,1 the designing engineer, which gives the details and costs of design and construction. The following changes have been made since that article was published:

Jan 8, 1919

By Sidney Sigel, J. Gardner Brooks, Irvin R. Kramer

In 1942 Grossmannl proposed that the hardenability of a steel may be calculated from its chemical composition by considering the base hardenability associated with its carbon content and grain size and multiplying this base by factors for each element present. Since Grossmann's original publication, several investigaton2-6 have reexamined the multiplying factors for the individual elements and in general have found that the multiplying principle is valid. However, some of the individual factor curves developed have been in poor agreement. Inasmuch as the carbon-factor curve obtained by Grossmann was dependent Lipon the factors for all the other alloying elements present in the steel, it logically followed that his results were in need of correction in the light of the new data available for manganese, silicon, and the other alloying elements. Furthermore, in order to avoid the possibility that errors in the manganese, silicon, or other curves might influence the carbon-factor curve, investigation of iron-carbon alloys containing little or no manganese and silicon was necessary. That the effect of carbon on hardenability was greater than indicated by Grossmann is shown by a comparison of the diameters of completely hardened rounds of iron-carbon alloys with the ideal critical diameter calculated from Grossmann's factors. These alloys have a greater hardenability in a finite quench than predicted by Grossmann's factors for an infinite quench (Table I). Among the other important variables that were in need of further investigation were the effect of deoxidation practice on the grain-size correction curves and the effect of stable carbide-forming elements on the depth of hardening. Most Of the work by Kramer, Hafner, and Toleman4 was done on silicon-killed steels. It was not known whether Gross-mann's grain-size correction curves, determined on aluminum-killed steels, was valid when applied to steels with different deoxidation practice. More data on the

Jan 1, 1947

By J. Gardner Brooks, Sidney Sigel, Irvin R. Kramer

In 1942 Grossmannl proposed that the hardenability of a steel may be calculated from its chemical composition by considering the base hardenability associated with its carbon content and grain size and multiplying this base by factors for each element present. Since Grossmann's original publication, several investigaton2-6 have reexamined the multiplying factors for the individual elements and in general have found that the multiplying principle is valid. However, some of the individual factor curves developed have been in poor agreement. Inasmuch as the carbon-factor curve obtained by Grossmann was dependent Lipon the factors for all the other alloying elements present in the steel, it logically followed that his results were in need of correction in the light of the new data available for manganese, silicon, and the other alloying elements. Furthermore, in order to avoid the possibility that errors in the manganese, silicon, or other curves might influence the carbon-factor curve, investigation of iron-carbon alloys containing little or no manganese and silicon was necessary. That the effect of carbon on hardenability was greater than indicated by Grossmann is shown by a comparison of the diameters of completely hardened rounds of iron-carbon alloys with the ideal critical diameter calculated from Grossmann's factors. These alloys have a greater hardenability in a finite quench than predicted by Grossmann's factors for an infinite quench (Table I). Among the other important variables that were in need of further investigation were the effect of deoxidation practice on the grain-size correction curves and the effect of stable carbide-forming elements on the depth of hardening. Most Of the work by Kramer, Hafner, and Toleman4 was done on silicon-killed steels. It was not known whether Gross-mann's grain-size correction curves, determined on aluminum-killed steels, was valid when applied to steels with different deoxidation practice. More data on the

Jan 1, 1947

By Richard E. Chism

Some years ago, when I was seeking an illusive fortune and gaining a precarious existence in the primeval forests of Brazil, there penetrated, even to my headquarters in that far-off land, the story of a new-found mining district, where mountain peaks were ribbed with silver, and valleys teemed with virgin gold. Such were the stories that caused hundreds of men to seek their fortune in Sierra Mojada, and to return heaping curses, loud and deep, upon the vivid imaginations that had evolved the glittering fiction. Nevertheless, the rumors had some foundation of truth. The ribs of silver exist, if not the placers of gold; and a flourishing town, of some three thousand people, with two leading mining companies and several smaller ones, in operation, represents what was permanent in the excitement of 1879. Geographical Situation. The town of Sierra Mojada is situated in the State of Coahuila, Republic of Mexico, in latitude 27' 24' N., and longitude 26' 40' W. of Washington, 4' 36' W. of the City of Mexico, and 103' 43' TV. of Greenwich. It lies about 70 miles, in an air-line, N. E. of Escalon station, on the Mexican Central Railroad; but by the present wagon-road, which makes a long detour to turn the mountain range, the distance to the station is about 105 miles. The nearest towns are Huajuquilla, in the State of Chihuahua, about 125 miles due west, and Cuatro Cienegas, in the State of Coahuila, 112 miles to the eastward. Between these points and the town of Sierra Mojada, and to the north of this town, the country is an immense desert, entirely uncultivated, almost uninhabited, and very little known. This

Jan 1, 1887

By Alden B. Greninger, Victor G. Mooradian

Microscopic examinations of quenched (beta) 60:40 copper-zinc and quenched (beta) 74:26 copper-tin alloys have frequently disclosed long, thin parallel bands or markings within the polyhedral beta grains. Apparently, it has been accepted that these markings are mechanical twin bands, although there is no published account of experimental data that might tend to substantiate this belief for the copper-zinc system, and only meager evidence has been submitted for the copper-tin system. Johnsonl0 commented upon the markings he observed after deforming a quenched brass of 55.6 per cent copper and 44.4 per cent zinc. Clark's papers4 on the heat-treatment of Muntz metal contain many photomicrographs of markings in beta brass; these she referred to as Neumann bands (inasmuch as repolishing and re-etching failed to remove them) and stated that markings present in Muntz metal as quenched were the result of shock imparted during the polishing operation. Van Wert18 first suggested that these parallel markings in quenched beta brass (60:40) might be alpha precipitated along certain crystallographic planes of the matrix lattice. He showed that upon reheating the specimens to temperatures below 800" C., obvious precipitation of alpha within the large beta grains first occurred at the markings. In a discussion of this paper, Phillips stated (pp. 505-507) that in his opinion the markings observed by Van Wert were mechanical twins resulting from contraction strains produced during the quenching operation. In a study of segregate structures in beta copper-tin, Smith17 observed that in the quenched beta phase (containing 74.92 per cent Cu) parallel . bands or markings very similar to those in metastable beta brass could be

Jan 1, 1938

By Alden B. Greninger, Victor G. Mooradian

Microscopic examinations of quenched (beta) 60:40 copper-zinc and quenched (beta) 74:26 copper-tin alloys have frequently disclosed long, thin parallel bands or markings within the polyhedral beta grains. Apparently, it has been accepted that these markings are mechanical twin bands, although there is no published account of experimental data that might tend to substantiate this belief for the copper-zinc system, and only meager evidence has been submitted for the copper-tin system. Johnsonl0 commented upon the markings he observed after deforming a quenched brass of 55.6 per cent copper and 44.4 per cent zinc. Clark's papers4 on the heat-treatment of Muntz metal contain many photomicrographs of markings in beta brass; these she referred to as Neumann bands (inasmuch as repolishing and re-etching failed to remove them) and stated that markings present in Muntz metal as quenched were the result of shock imparted during the polishing operation. Van Wert18 first suggested that these parallel markings in quenched beta brass (60:40) might be alpha precipitated along certain crystallographic planes of the matrix lattice. He showed that upon reheating the specimens to temperatures below 800" C., obvious precipitation of alpha within the large beta grains first occurred at the markings. In a discussion of this paper, Phillips stated (pp. 505-507) that in his opinion the markings observed by Van Wert were mechanical twins resulting from contraction strains produced during the quenching operation. In a study of segregate structures in beta copper-tin, Smith17 observed that in the quenched beta phase (containing 74.92 per cent Cu) parallel . bands or markings very similar to those in metastable beta brass could be

Jan 1, 1938

By F. E. Lathe, L. Hodnett

This paper summarizes extensive data supplied by 40 copper converter plants in 18 countries, and includes a partial analysis and comments on the effect of converter slag composition and temperature on the fomzation and elimination of magnetite and the life of basic and neutral refractories. APRELIMINARY draft of this paper, including data from 26 companies which had submitted replies to a questionnaire, was presented at the Annual Meeting of the AIME held in New York in February, 1956. Publication was delayed in the expectation that additional replies would be received, and justification for the subsequent delay may be found in the fact that the present revised paper contains data from 40 converter plants situated in 18 different countries. The suggestion that a questionnaire be sent to the major copper and copper-nickel plants outside the U.S.S.R. and associated countries arose at the Los Angeles Annual Meeting in February, 1953, where several papers dealing with converter construction and operation were presented. In private discussions which followed, a group of metallurgists and refractories engineers raised the question why practices varied so much at different plants. Why did magnesite brick give superior service to chrome-magnesite in some plants but chrome-magnesite prove superior in others? Would metallurgical studies point the way to the development of still better refractories? Could magnetite formation be prevented in converter slags and reverber-atory furnace mattes? If this was feasible, why was a heavy circulating load of magnetite tolerated, when, in all probability, it increased copper losses in the reverberatory slags and, in some cases, made it necessary to shut down the furnaces periodically to clean out the accumulated magnetite? Was the sole purpose of coating brick with magnetite that of

Jan 1, 1959

By K. H. Heino

Two 200 T/da Lurgi Turbulent Layer fluid-bed roasters have been in operation at Canadian Electrolytic Zinc Limited since 1966. Zinc concentrate containing 52-54% Zn, 9-11% Fe,31-33% S is treated to produce calcine containing 60-62% Zn,10-12% Fe, .l-.3% S as sulphide and .8-1.2% S as sulphate. Each roaster train comprises a waste heat boiler, two cyclones in parallel and a two-field electrostatic precipitator. Distribution of calcine collected is 10-15 percent from bed overflow, 55-65 percent from boilers, 20-25 percent from cyclones and 2-6 percent from precipitators. A Monsanto designed contact plant produces acid at a rated capacity of 365 T/da (100% H2304 basis) from roaster gases diluted to 7.0-7.5% S02. The process steps are gas cleaning and cooling by weak acid scrubbing, acid mist removal in electrostatic precipitators, gas drying in 93.5-96.5% H2304, conversion of sulphur dioxide to sulphur trioxide in a four-pass converter containing vanadium pentoxide catalyst, and absorption of the sulphur trioxide in 98.1-98.3% H2S04. Product acid is 93.2% H2S04. Conversion efficiency is 97-98 percent and overall sulphur recovery from concentrate is 87-90 percent. The adjacent fertilizer plant has a capacity of 135 T/da of P205. The products are 54 percent phosphoric acid, run-of-pile triple superphosphate, and diammonium phosphate. The plant is of Ugine-Kuhlman design and consists of an air-cooled multiple tank reactor, a tilting pan filter, and a forced circultation vacuum evaporator. Triple superphosphate is made on a continuous belt and partially cured in a rotary dryer. Diammonium phosphate is produced by ammoniating phosphoric acid in a single stage reactor. The slurry of ammonium phosphate is granulated in a blunger and dried.

Jan 1, 1970

By Lyman Taylor, Alexander R. Troiano

STUDIES of the transformation of austenite at constant subcritical temperatures have been numerous since the work of Davenport and Bain.1 Considerable information has been obtained on low-alloy steels and on high-carbon alloys containing undissolved carbide or graphite at the austenitizing temperature. Little is known of the isothermal transformation of austenite containing in solution large amounts of both carbon and a single alloying element. In this investigation four steels containing one per cent carbon and with chromium in the range 3 to 9 per cent have been examined with the view to establishing the fundamental character of the isothermal reactions when all carbon and chromium are initially in solution in austenite. EXPERIMENTAL PROCEDURE Alloys The chemical compositions of the steels investigated are given in Table I. The 4 per cent Cr alloy is a commercial steel. The other steels were made by the Carpenter Steel Co. as 50-lb., induction-furnace heats and rolled to 5/8-in. round bars. Bars were softened at 650° to 700°C. before the specimens were cut. [ ] Metallographic Method Most of the lines on the transformation diagrams presented here have been placed on the basis of the microscopic examination of partially reacted specimens. Thees specimens were approximately ½ by ¼ by 1/8 in. in size. Specimens of the 9 per cent Cr steel were held 10 to 12 hr. at 1200° to I225°C. before quenching to the various subcritical temperatures. The other steels were held for 2 to 2 ½ hr. at 1200°C. before quenching. These treatments, carried out in an atmosphere of purified nitrogen, produced an austenite grain size larger than A.S.T.M. No. I, some grains being 1 to 2 mm. in diameter. There were a few undissolved carbide particles in some specimens of the 9 per cent Cr steel. It is believed, however, that any errors in the results due to incomplete solution of carbon and chromium in austenite are negligible; that is, austenite compositions may be considered as being those listed in Table I. X-ray Methods Constituents were identified and martensite axial ratios determined from Debye

Jan 1, 1945

By F. E. Bash

CONSTANTAN is an alloy of copper and nickel that is extensively used, under a number of trade names, as a resistance wire with a low temperature coefficient of resistance, and one of the elements of base-metal thermocouples, iron usually being the other thermoelement, although for low-temperature work copper is also used. Before the war, constantan was imported, in common with many other technical necessities. Since it required considerable time to receive the constantan after it was ordered, fairly large stocks were kept on hand; but after the beginning of the war no more was imported acid the stocks of foreign material were exhausted about the same time that the steel and munition manufacturers began to need great quantities of it for thermocouples for the heat treatment of steel. To meet this demand, the International Nickel Co. began manufacturing constantan that met all the requirements of the users of resistance wire but did not give the same electromotive force against iron as the German material and consequently could not be used with instruments calibrated for a definite e.m.f.-temperature relation. It so happened that all the constantan made had an e.m.f. lower than that necessary to meet the specifications of the Leeds & Northrup Co. for whom this investigation was carried out. If some had been higher and some lower, good wire could have been obtained by a, process of selection, but as it was no wire at all could be procured. To remedy this situation, a thorough investigation was started with the close cooperation of the International Nickel Co. and the Electrical Alloys Co. The specifications to which the constantan had to conform were that it should give an e.m.f. of 47.40 millivolts. against pure iron at 1500° F. (816° C.) with the cold-junction temperature at 0° F., or a proportional e.m.f. at temperatures near 1500° F. The method of checking a wire was as follows: It was first welded to a piece of iron wire; Armco iron was found to be satisfactory but iron with greater than 0.1 per cent. carbon would give a lower e.m.f. against the same piece of constantan than pure

Jan 9, 1919

By Bror Nordberg

SAND and gravel are unconsolidated granular materials resulting from the natural disintegration of rocks. The two materials nearly al- ways occur together, variably proportioned in widely available de- posits. A commercial sand comprises the fine granular material, usually less than f in. in diameter (ASTM Designation C58-28), and gravel consists of the coarse, granular material larger than sand (ASTM Designation C125-46T). Gravel falls within the range of 1/4 in. and a top size usually of 3 ½ in. Chemical definition is impossible. Sand and gravel are always of secondary origin. They were formed from various massive rocks through the action of chemical and mechanical forces; then transported, abraded, washed, sorted, and classified by streams, glaciers, waves, or winds, to be redeposited in beds as they are found. Chief disintegrating forces in the reduction of rocks into granular particles were frost, rain, the dissolving action of acid and alkaline ground waters, the mechanical action of streams and waves, and the action of glaciers. Method of formation and deposition have imparted physical properties to sands and gravels that largely determine the commercial value of the materials for particular use and influence the manner of exploitation. In the early days of the commercial industry, purchasing specifications were relatively lenient but in. the past decade much more rigid quality requirements have had to be met for acceptance by all classes of purchasers. The trend to further severity in requirements is a challenge to the industry that commands full knowledge of the nature of raw materials at hand and skillful application of processing into commercial products. Mechanical strength, the ability to resist disintegration, chemica

Jan 1, 1949

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

By AIME AIME

THE PAPER, "Surface Effects on Assay Beads Caused by Metals of the. Platinum Group," presented by J. L. Byers, before the Institute of. Metals Division at the February meeting of the Institute, is the subject of interesting discussion, an abstract of which follows. The original paper is available at Institute headquarters as a Preprint. Member-What assurance have you that the percentage of metals, as stated, is really an accumulation?

Jan 1, 1932

By Wheeler Davey

WHEN metals are subjected to mechanical working, such as rolling, one of the phenomena that take place is a movement of the crystals of the metal into a system or systems of orientation which bear an angular relation to the direction of working. In rolled metal the crystals may orient themselves with respect to the rolling plane or the rolling direction, or both. Direct evidence of the existence of preferred orientations in rolled metal has been obtained by numerous investigators from X-ray patterns of the rolled metal. Most of these workers used a monochromatic pinhole method. Where the degree of preference for a single orientation is high the monochromatic pinhole pattern may be interpreted by a geometrical calculation based on the angular relationships of the planes in the crystal and the diffraction arcs on the X-ray pattern. This process may be aided by the geometrical construction of the locus sphere (Langenkugel), and reflection circles of Polanyi,1 Polanyi and Weissenberg,2 and Mark and Weissenberg,3 and of the plane polar figures (flachenpolfigur) of Franz Wever.4 R. M. Bozorth5 solves X-ray patterns from metals having a single preferred orientation by means of a series of charts which when placed over the X-ray pattern give directly certain angular relationships, between the crystal planes and the surface of the specimen.

Jan 1, 1929

By O. H. Eschholz

The electrostatic process of fume precipitation is an excellent example of the successful application of scientific knowledge to an industrial operation. Originally proposed for the precipitation of sulfuric acid mists, it has been extended until at present there is practically no fume-carrying gas to which the method cannot be applied. Among the more common applications are: the recovery of non-ferrous smelter flue-dust, iron blast-furnace dust, cement dust, and potash fume. It should be borne in mind that the process is restricted to the precipitation of suspended particles, either liquid or solid, and does not separate gaseous constituents. However, by proper temperature control, mixtures of vapors having different temperatures of condensation to either solids or liquids may be selectively precipitated. The process consists essentially of subjecting suspended particles, including those too minute to be effectively acted upon by centrifugal or gravitational forces, to such an electrical force that they are driven from the gas stream, acting as a conveyer, and deposited upon a suitable receiving surface. This directional impulse is obtained from the interaction of charged particles and an electrostatic field of definite intensity gradient existing between two dissimilar electrodes, known as discharge and receiving electrodes. In principle, the equipment is equally simple. As shown diagrammatically in Fig. 1, it consists of: (1) A source of high-potential direct, current,, requiring: (a) Source of alternating-current energy. (b) Means of transforming from low voltage to high voltage. (c) Means of converting alternating to direct current. (2) Precipitation chamber having: (a) Transmission tubes for fume-laden gases. (b) Suitably designed and disposed electrodes. (c) Means for affecting removal of deposited solids. Although Hohlfeld demonstrated, in 1824, that a smoke-laden atmosphere could be cleared by applying an electrostatic field, and while Sir

Jan 1, 1919