Search Documents

By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By Samuel G. Lasky

What the evidence prevails upon the mind to believe, depends upon the mind as well as upon the evidence. M. L. IN a recent discussion of the mineral resource position of the United States, published in the September 1946 issue of MINING AND METALLURGY, I expressed my conviction that ore deposits of major magnitude remain to be found in this country and that they can be found without undue cost or risk. I stated with equally strong conviction, however, that if the search for such deposits is to be notably successful there must be, among other things, a reorientation of philosophy and mental habits on the part of many who would be connected with the search. I would now like to enlarge upon that statement. For such a purpose, we may consider that the search for concealed deposits involves four steps: (I) the selection of areas for further study; (2) the geologic study of those areas in order to verify their general favorableness and in order to choose specific patches worthy of being tested; (3) the decision whether exploration of the patches chosen should actually be undertaken; and (4) the exploration itself. The first two steps and the last rest upon the judgment and skill of geologists. The third step-the decision whether exploration should be undertaken-rests upon management. In my opinion, the philosophies or principles that have guided these steps in the past are now inadequate. PHILOSOPHY OF APPRAISAL If concealed deposits are to be looked for, how are the places of their possible concealment to be recognized? Every known mineralized area still in the prospect stage has already been repeatedly examined and condemned. As for those deposits concealed under later rocks, there may be not even the clue of a near-by outcrop for engineer or geologist to consider. How then, are we to know where to look? Geologic Probability In the early days of our mining industry, ore deposits were found mainly by "following the ore." Later, as such opportunities decreased, and as geologic concepts became accepted, deposits were found more and more through use of the notion of geologic probability. Many instances can be cited wherein a courageous operator ignored the implications of the unsuccessful efforts of predecessors and, solely by "following the ore," converted a discredited prospect into a good mine. Similar experience doubtless will occur in the future, but "following the ore" will no longer in itself find new deposits in the amount needed. Nor can enough new ore be expected from further use of the notion of geologic probability, for, as mentioned above, our known prospects `have already been ex-

Jan 1, 1947

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By P. Farrar, H. Margolin

The Ti-Pb diagram was investigated in the region 0 to 58 pct Pb and from 500°C to liquidus temperatures. Three reactions were encountered: I—ß?a+Ti Pb at 725 10°C; 2—ß+L?Ti4Pb at 1305+ 10°C; and 3—the possible eutectic L-+Ti,Pb and y between 1200" and 1300°C. LEAD-RICH alloys have been investigated by Nowotny and Pesl,' who used sintered compacts and studied the region from 37.5 to 100 pct Pb by X-ray diffraction analysis. The only phase found in addition to titanium and lead was the hexagonal compound Ti Pb. Alloy systems of lead with metals of the transition group, such as iron, chromium, tungsten, cobalt, nickel, or manganese, generally show little liquid or solid solubility.' Craighead et al.,3 however, indicated that lead is soluble in a and ß titanium to at least 2.1 pct. They also found that approximately 50 pct of the lead added was lost during the arc-melting of Ti-Pb alloys. In the present investigation, are-melting also was used to prepare Ti-Pb alloys and similarly large lead losses were encountered. Experimental Procedure Alloy Preparation: Considerable difficulty was encountered in the melting of the Ti-Pb alloys and a number of experiments were performed before the method described was developed. Alternate layers of lead and titanium were wrapped with titanium sheet and compacted. This "sandwich" was annealed at 300" to 350 °C and was melted according to the procedure described by Cadoff and Nielsen.' Using a low current, 150 amp, and an argon atmosphere, four to eight 10 to 20 sec melts were made on each alloy, with the button being turned over between each melt to insure homogeneity. In the high lead range, the preliminary sintering was found to be of doubtful value and was eliminated. In the region above the nominal composition of 70 wt pct Pb, the alloys prepared in this manner always consolidated into two phases. The outside appeared to be composed entirely of lead and the inside was a Ti-Pb alloy. In order to determine whether this phenomenon was caused by a miscibility gap, master alloys with a nominal composition of 40 wt pct Pb were machined and mixed with various percentages of lead sheet. This mixture was compacted and melted in the same manner as the other alloys. Although these alloys were not homogeneous, they did not show the layering that was observed

Jan 1, 1956

By Paul Averitt

The U. S. Geological Survey has been actively engaged in work on coal for more than 50 years. During this long period we have released more than 300 publications containing information about coal and coal reserves, including details on the thickness, distribution, and quality of coal, and the structure and stratigraphy of the coal-bearing rocks. We have also cooperated with state surveys on many similar publications. For many areas these reports are the only reliable published data on our resources of coal. During the last several years we have substantially increased our activities above the wartime low. We now have field work in progress, or reports in preparation, on 13 detailed mapping projects distributed as follows: 1. Pennsylvania anthracite field 2. Casselman Basin, Md. 3. Leslie County, Ky. 4. Deep River field, N. C. 5. Coosa field, Ala. 6. Powder River field, Mont. 7. Spotted Horse field, Wyo. 8. Yampa field, Colo. 9. Paonia field, Colo. 10. Trinidad field, Colo. 11. Durango field, Colo. 12. Chaco River area, N. M. 13. Lewis and Thurston County fields, Wash. For two of these areas; the Paonia field, Colo., and the Coosa field, Ala., we have published recently preliminary reports, and final reports are in preparation. In addition, we are nearing completion of a coal reserve study of Montana, and are beginning similar studies in several other states, as part of a program of revising our estimate of national coal resources on the basis of presently available data. Factors Involved in Making Estimates Our responsibilities include detailed field mapping to secure information on areas of outcrop of coal beds, their range in thickness, nature of roof rock, amount of overburden, correlation of the beds, stratigraphy and structure of the coal-bearing rocks, and the preparation of coal reserve figures based on these data. The computation and estimation of resources of coal in the ground, like that of resources of other mineral commodities, involves consideration of many additional purely geological factors that can be appraised best through such regional studies. Regional variations in the thickness and texture of rocks overlying and underlying coal beds, for example, give evidence as to the probable position of the edges of the basin of coal deposition, or may aid in the delineation of sand-filled channels that sometimes cut out coal beds. It is apparent that the detailed field studies, in which data are gathered, are the basis for coal reserve studies, and in our present program these two phases of work are being carried on together. Previous Coal Reserve Estimates For many years we have been aware

Jan 1, 1950

By John Chipman, Theodore B. Winkler

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By Theodore B. Winkler, John Chipman

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

department, first as a practical miner, next. as rodman on the survey corps, of which he soon became chief, then draftsman and mining engineer in the company's office. In January, 1916, he was promoted to the position of district engineer in charge of mining engineering work. He became a member of this Institute in September, 1917. Captain Ba.llamy's military experience began at the same time as his engineering practice. He was a charter member of Company A, Engineers, N. G. P., which was organized ten years ago. He saw service on the Mexican border as First Lieutenant of this Company, and remained in that position until November, 1916. In July, 1917, he was again called into service and was sent to Camp Hancock, Ga., with the 103d Regiment of Engineers. Before joining this regiment he attended a school for officers at Fort Sill, Okla., where he received special training in field fortifications. In December, 1917, he was commissioned Topographical Captain on the Regimental Staff, and in April, 1918, preceded his regiment by about six weeks to France, where he again attended an officers' training school. He rejoined his regiment on July 15, near Chateau Thierry and was killed near Fismes on Aug. 9, 1918. Lieutenant Martin F. Bowles Martin F. BOWleS, born Apr. 25, 1893, at Bonne Terre, Mo., and graduated from the Neodesha, Kans., High School, had finished all but one month of a four-year course in metallurgical engineering at the Missouri School of Mines, Rolla, Mo., when on May 12, 1917, he entered the first Officers' Training Camp at Fort Riley, Kans. At the close of the training period, he was commissioned a Sccond Lieutenant and assigned to Co. B, 355th Infantry, 89th Division, and stationed at Camp Funston. He left this camp with his company on May 21, 1918, and sailed from an eastern port on June 4, ayriving in England on June 15, 1918. After a short stay at a rest camp there, he proceeded to France. On August 14, he wrote that he was with Battalion Headquarters as Gout Officer, 1st Battalion, 355th Infantry, 89th Division. The last letter received from him, dated September 2, was written in his dugout and contained the following: "Here it is 2.45 a. M. Sitting in a dugout waiting for some patrols to report back in, I am writing this by the light of two candles." He was killed in action on the night of Sept. 3, 1918. The letter of notifi-

Jan 1, 1920

By V. C. Allen

THE Tri-State Zinc, Inc., Galena, Ill., was confronted with the problem of securing ore from a deposit because the hoisting shaft was several thousand feet from the mill. The orebody is several thousand feet long, averaging 200 ft in width and 60 ft in height and opened up by vertical shafts some 300 ft deep. Mining is by the room-and-pillar method. During the initial operation the ore was loaded by conventional electric 1/2-yd boom-and-dipper shovels and hauled to the shaft by 8-ton diesel trucks. This underground ore loading and hauling was well adapted to the conditions and productive of low costs per ton. However, with the mill situated as mentioned, a triple handling of all broken rock was necessary: l—from the stope to the shaft by truck, 2—up the shaft by skip br can into the surface hopper, and 3—by truck from the surface hopper to the crushing plant at the mill. In addition to the repeated handling, serious troubles were encountered during the winter because of freezing in the shaft hopper. Consideration was given to either moving the mill to the new orebody or to the construction of a second mill. The presence of other orebodies to be mined at a later date made the first alternative impractical while the capital outlay for a second mill, when the present plant of approximately 850 tons per day was deemed sufficiently large for the total reserves, made the second alternative also unwise. It was decided to retain the mill in the originals location and continue to move the ore to it. The idea of driving an inclined adit from the surface to the bottom of the orebody suitable for truck haulage and big enough to allow the passage of all mechanical equipment was conceived. Among the apparent advantages of such an incline were: 1— Direct haulage from the stope to the mill without rehandling. 2—Elimination of virtually all grizzlies. Trucking from underground to the mill would do away with all hoppers, chutes, gates, and skips and make the maximum rock size dependent solely on the size of the shovel dipper at the mine and the crusher opening at the mill. 3—Less secondary blasting would be needed. 4—Ease of transporting equipment and supplies underground. Shovels and trucks could be taken through the incline intact. 5—Equipment could be brought to the surface for repairs and servicing without loss of time. The same advantages of ease in moving would be present in the handling of men, steel, powder, and supplies. 6—There would be far less difficulty in increasing the amount of tonnage that could be moved by truck up an incline than would be found in attempting to increase the capacity of a shaft. 7—All the broken ore in the stopes would serve as bin capacity, as it would take the breakdown of all of the loading and hauling equipment to have the same effect as a delay in shaft hoisting. 8—All danger of men being trapped in the mine as a result of shaft fire or power stoppage would be eliminated. 9— Virtually all trouble from severe winter conditions would be eliminated by the direct haul underground to the mill. The decision was made to proceed with the driving of an inclined adit. The topography of the surface between the orebody and the mill was such that it was possible to locate the portal at a point 170 ft above the mine floor and 1800 ft horizontally from the central point of the orebody to the south and 2500 ft from the mill to the north. A grade of 10 pct was found to be optimum for continuous truck haulage when the various factors of speed, safety, and truck maintenance were all considered. The incline as driven was consequently 1700 ft long on 10 pct grade and 12 ft high by 17 ft wide in cross section. The tunnel-driving equipment was chosen so that it could be used in mining after the completion of the tunnel. Drilling was done with a jumbo with two Joy jibs mounting 3-in. drills, loading with an Allis-Chalmers diesel-powered, front-end loader of approximately 11/4-yd capacity, and hauling by Koehring Dumptor trucks of 8-ton capacity, diesel-powered. The width of the tunnel allowed the end loader and Dumptor to be placed abreast. Since the Dumptors can be driven either forward or backward with equal facility, loading was accomplished without turning around either machine throughout the loading operation. The crew in addition to the tunnel foreman was comprised of three men per shift at the start and in the later work, four men. Each crew could perform any part of the working cycle. If the drilling was completed and the round blasted in the middle of a shift, the same men would proceed with the loading and hauling. Since the mine already had been drained to the bottom levels, no water was encountered. At the halfway point the tunnel was widened for approximately 100 ft to permit trucks to pass. The total cost of the tunnel excluding the capital outlay for equipment, which was all continued in use in the subsequent mine operation, was $60,363.00 or $35.50 per ft. The tunnel was completed at the end of June, 1949 and has been in continuous use since that time. In the five months from July to November inclusive, 106,049 tons have been transported to the mill or an average of 835 tons per day. No unforeseen disadvantages have been encountered and the advantages which had been predicated before the adit's construction have been more than realized. As previously mentioned, the deposit is worked by the room-and-pillar system with occasional faces up to 125 ft high. Except in driving development drifts when diesel-powered, front-end loaders such as were used in the tunnel are employed, all shoveling is done by Yz-yd boom-dipper type shovels electrically driven. These units need a width of 25 ft and a height of 14 ft in which to operate. All hauling is by diesel trucks, mainly Koehring Dump-tors. Roads are maintained with caterpillar tractors and a road grader. The tonnage output from the

Jan 1, 1952

By Wilbert G. McBride

Two Also 3 1/2-ton motor trucks were used by Young Bros. while operating at the Mammoth Collins mine at Shultz, Ariz. One was equipped with an oil tank holding 1,075 gal. and was used for the transportation of "tops." The other was fitted with a stake body and used to carry machinery, wood, rails, pipe and all classes of miscellaneous supplies. The bodies were made of oak with maple flooring and were attached to the frame of the chassis by U-bolts, to avoid drilling the main members of the frame. Most of the hauling was done from Tucson, a distance of 47 1/2 miles. During the first 3 months, part of the road was in very bad condition and the tire cost was excessive. After this part was repaired the road was in fair condition, but never good. There were no excessive grades or bad sand, but wagon ruts, too narrow for the truck wheels and of a different gage, caused heavy tire loss; while chuck holes, sharp curves and stones, both imbedded and loose, were objectionable features. During wet weather the trucks could not get sufficient traction to climb some of the hills and were likely to stick in the mud in certain places, so that no attempt was made to run them unless they were on the' road when the rain started. This lost time amounted to about 5 per cent. of the total, but, whenever possible, it was utilized in making minor repairs. The price of gasoline was from 17 to 21 c. per gal. Rubber tires were used throughout. Drivers were said $4.50 to $5 per shift, and a return trip to Tucson was counted as two shifts even when made in one day. Drivers were provided with a room in Tucson and were paid for a11 time lost due to causes beyond their control. Trucks were loaded one way only. Speedometers were placed on both trucks but the excessive vibration soon caused them to fail. For this reason, and because no account was taken of the distance covered in picking up a miscellaneous load or in other minor ways, the mileage given is under the actual distance traveled. Some of the weights had to be estimated, but care was taken to have the number of ton-miles low rather than high, to avoid underestimating the costs. The cost of hauling from Tucson to the mines was $12 per ton

Jan 1, 1917

By D. S. Hutton, W. C. Leslie

Thermal etch patterns developed on poly crystalline 3.5 pct Si-Fe by heating in hydrogen or in argon have been examined. The most prominent feature of the etching is the development of striations on grains with (100) planes near the plane of the surface. These striations are probably produced by the resoution of a random, high-energy plane into (100) facets of lower energy. THE thermal etching of iron and iron-base alloys has a long history. The phenomenon was observed by Osmondl more than 70 years ago. The literature on thermal etching between that time and 1951 was reviewed by Olney,2 and a briefer review appeared in 1958. 3 The only articles which have been found dealing with the thermal etching of silicon iron are those of Dunn and Lionetti4 and of Dunn, Daniels, and Bolton,5 and they reported only grain boundary etching. EXPERIMENTAL PROCEDURES A cast 3.5 pet Si-Fe alloy was given a metallo-graphic polish and etch, then placed in flowing purified hydrogen for 6 hr at 2200°F. The same specimen was later repolished and etched to remove the thermal etching. The specimen was then held in flowing purified argon at 2200°F for 72 hr. In both instances the specimen was rapidly cooled by being pulled up quickly into the cold zone of the furnace. All photomicrographs shown are of the surface as removed from the furnace. Oblique illumination was essential for observation of the thermal-etching effects with a light microscope and was used for all the photomicrographs. RESULTS AND DISCUSSION Grain boundary etching, grain boundary movement, and contouring within grains are illustrated in Fig. 1. The contours within a single grain followed behind the advancing grain boundary. To determine the average contour interval, or step height, white light was used in an interference microscope. The steps were of the correct magnitude to separate while light into its spectrum of colors. A green light was focused at the top of a contoured area, shifting to red across the field. By using the difference in the dominant wave length of red and green light,6 and counting the number of steps across the area, it was possible to obtain a value of about 80A for the average step height. Laue back-reflection patterns of four grains with contour lines showed that the grains had a (100) plane slightly inclined to the plane of the surface (± 5 deg). Insofar as this could be determined from their irregular traces, the contour lines within a grain had a common direction, <100> ± 5 deg.

Jan 1, 1961

By A. K. Mukherjee, J. E. Dorn, J. D. Mole

Investigations were carried out on the effect of polyslip on the strain hardening of aluminum single crystals. The orientations investigated were those lor which the tensile axis was in the [001], [111], [112], and [012] directions plus another for which the Schmid angles for {111}(110) slip were 1 deg. The experimental data were analyzed on a model based on the intersection of dislocations with particular emphasis on the effect of polyslip on the activation volume for inter-section. It is shown that the rate of strain hardening inreases for those orientations wherein attractive dislocation intersections occur and that those orientations which produce the greater number of such intersections exhibit the greater strain hardening. Good correlation of the data is obtained with the concept that attractive junctions, as proposed by Saada, Play an important role in accounting for the rate of strain hardening. EXISTING concepts on the nature and cause of strain hardening in fcc metals have been deduced principally from experiments on the deformation of single crystals under single slip. The effect of crystal orientation on the shapes of the stress-strain curves for single slip have been summarized by seegerl and more recently by Clarebrough and Hargreaves.2 Tensile specimens whose axes fall near the center of the [001]-[011] line of the standard triangle of the stereographic projection exhibit the longest range of easy glide (Stage I) and the lowest rates of linear hardening (Stage 11) whereas specimens whose axes lie near fie [001]-[111] line of the standard triangle have limited or no easy-glide range and exhibit somewhat higher linear strain-hardening rates. Specimens whose axes lie near the [001] or the [ill] poles do not exhibit easy glide and have the highest rates of linear hardening. Kocks3 has shown that the highest rates of linear hardening Occur under Polyslip when the tensile axis coincides with the [111] or the [ 001] pole. Since the rate of strain hardening is sensitive to specimen orientation and the incidence of polyslip, these relationships might help to discriminate between various dislocation models for strain hardening in fcc metals. Previous attempts to analyze the effect of orientation on strain hardening,1"3 however, did not provide a unique answer to this problem. Consequently the present investigation was undertaken wherein additional data, particularly that for the effect of polyslip on the activation volume for intersection, was also determined in order to provide more complete information on the details of strain hardening. Whereas analyses of these data reveal that several recommended models for strain hardening are at variance with the facts, good correlation of the data is obtained with the concept that attractive junctions4 play an important role in accounting for the rate of strain hardening. I) EXPERIMENTAL APPROACH seegerl demonstrated that slip in fcc crystals at low temperatures is dependent on thermally activated intersection of glide dislocations with forest dislocations. This has been confirmed by tests on single crystals of aluminum by Mitra, Osborne and Dorn5 and on polycrystalline aluminum by Mitra and Darn.&apos; Thus in accord with Seeger&apos;s theory, the shear strain rate, ?, below a critical temperature, T, is where .V is the number of points of contact per unit volume between forest dislocations and glide dislocations, A is the area swept out per successful intersection, b is the Burgers vector, v is the frequency of vibration of the segment of the glide dislocation undertaking intersection, U is the activation energy for intersection, k is Boltzmann&apos;s constant, and T is the absolute temperature. For aluminum, which has an extremely high staeking-fault energy, the constriction energy is negligibly small and therefore the activation energy decreases practically linearly with the stress according to as will be recomfirmed later, where Uo is jog energy at the absolute zero, G and Go are the shear moduli at the test temperature T and O°K, respectively, L is the spacing of the forest dislocations, t is the applied shear stress for slip, and tGo is the stress field that must be surmounted athermally.

Jan 1, 1965

By B. H. Caudle, L. H. Silberberg

Reservoir depletion by natural water drive is typified by the movement of water from an aquifer into the adjacent oil-bearing formation. Prior studies of this type 01 water movement have generally neglected the resistance to flow in the aquifer and its effect on the movement of water into the oil bearing zone. A method for designing and operating scaled models of such reservoir systems is presented. Experimental data on a model of an edge-water-drive reservoir are shown and discussed. INTRODUCTION Most petroleum reservoirs derive at least a part of their productive capacity from water influx. This water may be injected from the surface or it may come from an aquifer adjacent to the oil zone. In either case, the reservoir engineer must be able to estimate the advance of the water as a function of either the elapsed time or the fluid produced. This paper describes a type of fluid flow model which includes the effect of viscous and gravitational forces in the reservoir and the surrounding aquifer. Natural water influx can be divided into three general (but widely overlapping) categories according to the direction of flow in the aquifer. These are shown schematically in Fig. 1. Fig. l(a) illustrates an edge-water-drive mechanism. In this case, water advances updip along the stratum but the movement of water is essentially horizontal and very little of the oil is actually underlain by water. The bottom-water drive (Fig. l(b)) is characterized by a thick aquifer underlying the oil zone. The water movement is generally vertical in the aquifer. The third category is illustrated in l(c). Referred to as the "thin oil column", this type of oil accumulation consists of oil over water in a relatively thin stratum. Fluid movement is horizontal in both the oil and water zones, except close to the producing well. One characteristic which all three of these types have in common is that part of the water flow takes place in the water invaded region of the oil reservoir while the remainder of the water flow occurs in the aquifer. The resistance to the flow of water usually will not be the same in these two regions. This occurs because the porous rock normally contains only water in the aquifer, while the water-invaded region always contains microscopic globules of bypassed oil (residual oil) which interfere with the flow of water through the rock. The production history of any type of a water-drive system is a function of two phenomena — where the water goes, and how it displaces the oil in the area invaded by the water. It is usually impractical to study these two phenomena at the same time. In most cases one type of analysis is used to predict the gross movement of water in the reservoir, while a different type of analysis is employed to determine the amount of oil to be recovered from the gross volume contacted by the water. The portion of the oil reservoir which is invaded by water is mainly a function of the resistances to fluid flow in the several parts of the flow system. This gross water influx in the three types of natural water drive typically results in water cusping to the production wells either from the side or from below (water coning). In 1747, Muskat described a greatly simplified mathematical model for predicting the area invaded by water in a bottom-water-drive reservoir.1 This model used the Laplace equation and suitable boundary conditions to describe the isopotentials and streamlines in the flow system. The use of this model assumes that (1) the reservoir rock is homogeneous in nature, (2) the oil and water mobilities are equal, (3) there is no oil flowing in the water invaded region, and (4) external forces — such as gravity — do not affect the flow. This method has been used for both natural water drives and water injection projects. In this, as in most models, the method of images is used to reduce the size of the model necessary to describe the reservoir. The assumption of equal viscosities and permea-

Jan 1, 1966

By W. G. Pfann

The simultaneous segregation of two solutes during the directional solidification of an ingot is treated mathematically on the basis of simplifying assumptions. Expressions are derived for the difference in concentration of two solutes, and for the location and concentration gradient of a pn barrier formed in a semiconductor by the segregation of a donor and an acceptor. THE problem of normal segregation of a single solute during the freezing of an alloy has been treated mathematically by a number of investigators. Gulliver&apos; showed that coring increases the quantity of eutectic above that to be expected at equilibrium, for a system having limited solid solubility and, on the basis of simplifying assumptions, calculated the fraction of eutectic to be expected. Scheuer2 expressed composition of solid solution in terms of a distribution coefficient and the fraction solidified and compared experiment with calculation for the systems A1-Cu, Al-Zn, Cu-Sn, Cu-Zn. Hayes and Chipman,3 in a detailed study of segregation in a low carbon, rimming steel ingot, calculated distribution coefficients for a number of solutes in iron, compared calculated and experimental segregation curves, and discussed the effects of process variables such as rate of solidification and stirring. In the present paper a mathematical analysis is made of the simultaneous segregation of two solutes during the orderly freezing of a solid solution system, with particular emphasis on the difference in solute concentrations. Although the analysis is quite general and can be applied to the segregation of minor elements in alloys, it is directed in particular at the solidification of a semiconductor containing a donor and an acceptor. Normal segregation has unique aspects in a semiconductor, because of the ways in which donors and acceptors affect the electrical properties. The difference between two solute concentrations becomes of importance, as does also the gradient of the difference where the difference goes through zero, this being the concentration gradient of excess carriers at a pn barrier. A primary object of this paper is to extend the mathematical treatment of segregation to include these newer aspects which are of particular significance for semiconductors. One property of interest is the electrical conduc- tivity, which arises from the presence of donors &apos;or acceptors in solid solution. The conductivity may be either n-type or p-type depending on whether donors or acceptors, respectively, are in atomic excess. For both germanium and silicon, elements of Group V of the Periodic System, such as P, As, and Sb, are donors and elements of Group 111, as B, Al, In, and Ga, are acceptors.4-6 If a donor or acceptor is present alone in solid solution, the conductivity is proportional to its concentration." If both a donor and an acceptor are present, then the conductivity is proportional to the difference in their atomic concentrations. If the donor and acceptor segregate at different rates then a pn barrier in certain circumstances may form at some point in the ingot. Accordingly, equations are derived and illustrated which express the effect of segregation on: 1—the concentration of a single solute with a discussion of the assumptions; 2—the difference between two solute concentrations and means for minimizing its variation in an ingot; and 3—the location and concentration gradient of a pn barrier. The analysis is applicable to processes in which the entire charge is melted and then progressively frozen from one end. The method in which an ingot is solidified in a crucible7 and that in which a solidifying rod is pulled from the melt8 both fall into this category. Segregation of One Solute If a cylinder of molten alloy is caused to freeze slowly from one end, a normal segregation of solutes will usually occur, producing a lengthwise concentration gradient in the ingot. Depending on whether a solute raises or lowers the melting point of the solvent, it will become concentrated in the first or last regions, respectively, to freeze. If it is assumed that freezing is such that there is no diffusion of solute in the solid, complete diffusion in the liquid, and that k, the distribution coefficient, defined as the ratio of solute concentration in the just-freezing solid to that in the liquid, is constant, then the

Jan 1, 1953

By R. L. Perrine

A stability theory is developed for miscible liquid-liquid displacement within a porous medium. In the usual case considered, a high-density high-viscosity "oil" is displaced downdip by a low-density low-viscosity "solvent&apos;! Perturbation methods are used to find the conditions under which the spreading mechanism changes from the stable dispersion process to unstable viscous fingering. We find that instability is conditional, that there is a dependence on the shape of a disturbance leading to a"diameter" effect and that very difficult experimental scaling problems may result. A useful consequence is the definition of a minimum "slug size" for stable miscible displacement. This should make possible optimum use of the solvent process for oil recovery. The results may apply to many situations in which one fluid displaces another of somewhat different fluid properties within a porous medium. INTRODUCTION The process of miscible liquid-liquid displacement looked very favorable when it first received serious consideration as a means to increase petroleum recovery. Some early laboratory results were interpreted to mean that only a small "slug" of solvent was needed, perhaps 2 to 3 per cent of a hydrocarbon pore volume. This "slug" could recover the oil in an entire reservoir provided the fluids remained miscible.1,2 Only a slow growth of the "mixing zone", or gradual transition from oil to solvent, should occur. This would follow naturally from mixing by a dispersion mechanism such as that described by Scheidegger.3 And, indeed, laboratory cores have shown this kind of behavior provided solvent viscosity was at least as great as that of the oi1.2,4-6 The same kind of behavior has also been observed with solvent viscosity lower than that of the oil after the distance traversed became large. Not all laboratory results have been this favorable, however.7-9 Mixing zone growth may become proportional to the distance traveled rather than the square root of this quantity. Such behavior accompanies high rates in short systems of large diameter, provided the viscosity ratio is adverse. If this more rapid spreading were to persist in a reservoir, the solvent requirement for miscible "slug" displacement could exceed 30 per cent of a pore volume. There is considerable economic importance in the difference between 3 and 30 per cent solvent. A 1ogical conclusion is that two different kinds of flow behavior are possible, with each kind leading to a different result. One kind gives efficient displacement, the other does not. In the efficient case, the solvent bank spreads out only by the mechanism we have termed dispersion. Under these conditions, displacement is as near piston-like as possible. In the second kind of flow, found only with adverse viscosity ratios, viscous fingering occurs. That is, permeability variations cause a small finger of low-viscosity solvent-rich fluid to move ahead of its average position within the mixing zone. This creates a path of low resistance to flow, and an even greater amount of solvent-rich fluid follows. Thus, the process is autocatalytic. Once started, the fingering mechanism rapidly becomes dominant. The question to be answered is this. Under what conditions will each of these two different kinds of flow occur? In particular, what conditions denote the transition from dispersion to viscous fingering as the solvent spreading mechanism? The answer may tell us whether or not the desirable, near piston-like miscible displacement process is practical. An answer to this problem can be obtained from theory by the use of perturbation methods. The procedure is as follows. We first formulate a mathematical representation of the system. Then a small disturbance (or perturbation) in solvent concentration profile is introduced and observed to see what happens. Unstable flow is indicated when a small disturbance will grow larger. This will lead to eventual viscous fingering. If on the other hand the disturbance dies out, the displacement is stable. In this latter case, with dispersion as the spreading mechanism, near piston-like displacement is possible. Thus, this paper presents the development of a stability theory for miscible liquid-liquid displace-

By R. F. Hehemann, Darrell W. Smith

The kinetics of alloying- in W-5 rot pct Re powder compacts were investigated at temperature about the upper limit for the formation of the x phase, such that a single intermediate phase was involved in the process. The rates and directions of motion of the a-o and o-b interface were assessed as functions of tinze at the sintering teri7peraticve by quantitative izetallog-ralhic techtziques. The iiotion 01 these interjuces could be specified approxitnate1.y by u Parabolic )-ate law and deviations from this ,rate law were attribuled to a complex interaction between surface dif&apos;fusion and volume diffusion during the initial stages of sintering. WHEN binary or more complex alloys are produced by sintering compacted blends of elemental powders, a complication is encountered which does not arise in the sintering of pure metals. In addition to concern for grain size and densification, the rate of inter diffusion of the component elements must be considered. The general problem of alloying during sintering has been treated by numerous investigators.&apos;-7 These investigations have been concerned only with systems that form continuous series of solid solutions and a concentric-sphere diffusion model4 provides a useful description of homogenization in these stems.&apos; Some controversy remains, however, over the contribution of surface and grain boundary diffusion to the homogenization process. Heckel% ePorts that homogenization can be described by volume diffusion at all temperatures, whereas other invetiators&apos;&apos; recognize the importance of surface and grain boundary diffusion, particularly at lower temperatures. Analysis of the homogenization process in partially miscible systems is complicated by the motion of the interfaces separating the individual phases. A simple analytical solution does not exist for such finite systems with spherical symmetry. It was the purpose of this work to examine the kinetics of the formation and dissolution of an intermediate phase in a binary system through an assessment of the motion of the interfaces separating this phase from the terminal solid solutions. PROCEDURE The W-Re system is an example of a partially miscible binary system and was selected for study because of its current importance in refractory-metal technology. The equilibrium phase diagram, Fig. 1, shows that the o phase will be formed by interdiffu-sion between tungsten and rhenium. At temperatures between approximately 2125" and 282O°C, the o phase will appear as the only intermediate phase in the diffusion system. In this work, a mixture of elemental powders containing 5 pct Re was employed. In such a mixture, the rhenium particles will be distributed randomly in a tungsten matrix. During sintering, a o-phase layer will form at the W-Re interface. The development and subsequent disappearance of the o phase are controlled by the relative rates and directions of motion of the 0-0 and a-p interfaces. The motion of these interfaces can be inferred from quantitative metallographic measurements of the average radii of the o shells surrounding rhenium particles. Elemental tungsten and rhenium powders of commercial purity were employed in these investigations. The rhenium powder was spheroidized from +200 mesh agglomerates by plasma-arc spraying and was then classified to yield a powder composed of essentially

Jan 1, 1967

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.&apos; The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By F. H. Wilson, E. W. Palmer

The solid solubility of iron in 2 to 10 pct cupro-nickels increases with temperature and nickel content. Property changes accompanying various heat treatments indicate typical precipitation hardening behavior. Iron content also affects softening temperature and sub-scale formation. These factors, as well as impingement corrosion resistance, influence the optimum iron content of commercial alloys. FOR many years Cu-Ni alloys have been used extensively in the form of tubes, pipes, and plates for the construction of salt-water lines and surface condensers on shipboard and in tidewater power stations. The 30 pct Ni alloy has been considered more resistant to rapidly flowing sea water than alloys of lower nickel content, and has been standard on ships of the U. S. Navy. Some ten years ago, the still better corrosion resistance obtained by modifying the 30 pct Ni alloy with approximately 0.5 pct Fe was recognized, and the iron-bearing alloy rapidly superseded the plain alloy as the standard material for severe service. In 1945, Tracy and Hungerford1 published a study of the effect of iron on the corrosion of various cupro-nickels in sea-salt solutions, and their data indicated that the 10 pct Ni alloy containing about 0.75 pct Fe was equivalent to the 30 pct Ni alloy containing 0.5 pct Fe. This was confirmed by LaQue in discussion of the above paper, and by results in an experimental condenser set up at the Kure Beach marine test station of The International Nickel Co., reported by Freeman and Tracy.&apos; The 10 pct Ni iron-bearing alloy is now being very widely used in applications where the 30 pct Ni iron-bearing alloy was formerly considered standard. While this "substitution" has undoubtedly been stimulated by the present extreme shortage of nickel, it must be emphasized that it involves no loss of service performance, and would have occurred anyway in the course of time, for economic reasons. In view of the increasing use of the 10 pct alloy, it seems desirable to make generally available the results of several investigations of Cu-Ni-Fe alloys carried out in the Metallurgical Research Laboratory of The American Brass Co. in recent years. The present paper, deals with the constitution of these alloys in the copper-rich corner of the system, and with the variations in hardness and tensile properties resulting from the heat treatment of alloys containing various amounts of iron. Most of this work is concerned with alloys containing 10 pct Ni. With over about 0.75 pct fe, the 10 pct Ni alloy is suscep- Alloys Several series of cupro-nickel alloys containing iron were used in these investigations. Most of them were prepared in the laboratory, but two samples of commercially fabricated alloys were included. Series A—Nominally 2 and 5 pct Ni, each with 0 to 1.5 pct Fe. Series B—Nominally 10 pct Ni with 0.1 to 0.4 pct Fe. Series C—Nominally 1.0 pct Ni with 0 to 2 pct Fe. Series D—Nominally 10 pct Ni with 3 to 5 pct Fe. Series E—Nominally 10 pct Ni with 1 and 1.5 pct Fe.

Jan 1, 1953

By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968