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By C. L. T. Edwards

IN the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on 100 per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blast-furnace charge as good iron as that made without scrap-made with straight ore?" This question may be answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on 100 per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. OPERATION WITH 100 PER CENT STEEL SCRAP During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a 100 per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when l00 per cent steel turnings were charged. Except for occasional charges of nickel scale as an "extra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore-ore and scrap-operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from i00 per cent scrap to the regular burden, the charge hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap charge. The furnace employed had a hearth 16 ft. 0 in., bosh 22 ft. 0 in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter ¾ in., bosh angle 73° 27' and a Baker-Neuman top, with gas-engine blowers. Analyses Range of Material Charged Gravel: Si02, 64.40 to .7o.54 per cent; A1203,3-52 to 4.58; CaO, 7.27 to 9.49; M90, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83.

Jan 1, 1941

By K. P. Gupta

In ternary systems containing silicon and transition elements, silicon was found to stabilize the a phase.1 At 1000°C a broad a-phase region was found in the Cr-Mn-Si system,1 which extends very close to the Mn-Si binary line (within about 3 at. pct Cr). Later investigation showed that, if chromium was replaced by small amounts (3 to 5 at. pct) of v,1 Ti, Nb, Ta, Mo, or w,1 the a phase or the R phase was again stabilized. Whether stabilization of complex crystal structures is possible by small additions of iron, cobalt, or nickel to Mn-Si is not known. Investigation of the Co-Mn-Si system4 shows the presence of several ternary phases, but at cobalt concentrations higher than 10 at. pct. In the present work the ternary systems Fe-Mn-Si and Co-Mn-Si were investigated at low iron and cobalt concentrations (< 7 at. pct Fe or Co) in search of phases of complex crystal structure. Experimental Procedure. The alloys were pre-pared by induction melting Co (99.8 pct), Si (99.9 pct), electrolytic Fe (99.88 pct), and Mn (99.9 pct) in recrystallized alumina crucibles under an inert atmosphere of argon gas. The alloy specimens were wrapped in molybdenum foil, sealed in argon-filled (at 1/2 atm) silica capsules and annealed for 72 hr at 1000" 1°C, and water-quenched. The use of argon-filled capsules was found to reduce the losses during annealing and the molybdenum foil prevented reaction of the manganese with silica. The total weight loss due to annealing and melting was found to be less than 1 pct for each alloy. The alloys were not analyzed chemically. A part of each annealed specimen was polished and examined metal-lographically using etching solutions, a) 0.1 to 0.5 pct oxalic acid solution in water, or b) 0.5 pct HNOs in methyl alcohol. Even though the etching solutions were quite dilute, the specimens were heavily etched and stained if the etching time exceeded more than 5 sec. Etching times found suitable were usually 1 to 3 sec. For X-ray diffraction work, a part of each annealed specimen was powdered by crushing after the exposed surface was ground off. X-ray diffraction patterns were taken with powder specimens using a 20-cm-diam asymmetrical focusing camera and Fe K radiation. These powder patterns were found quite satisfactory for the purpose of phase identification. However, X-ray diffraction patterns of single-phase alloy powder specimens were also taken using a Siemens diffractometer and filtered Cr-Ka radiation for greater resolution of the diffraction lines. Results and Discussion. In the Fe-Mn-Si system a new ternary phase was found at 1000°C between the p manganese and the MnsSi phase regions. The approximate phase relationships in this region of the 1000°C isothermal section are shown in Fig. 1. The new ternary phase, designated as the K phase, was found to occupy a narrow region about 1 at. pct in width and extending from Fee.oMn74.5Silg.5 to Fe.Mn.Silg.. At the high-iron content region, the K phase was found in equilibrium with the p manganese and the MnsSi phases but, at the low-iron content end of the K-phase region, the phases in equilibrium with the K phase were the p manganese phase, the MnsSi phase, and another new phase, designated in Fig. 1 as the v phase. The v

Jan 1, 1964

By P. P. Gregory

The rate of drilling operations in the West Texas district during 1940 was approximately equal to that of 1939. The total number of wells dillled in the area during the year was 1834, of which 1716 were completed as oil producers, 12 were gas wells and 106 were dry holes. The number of wildcat wells drilled during the year was comparatively small. The drilling of inside locations in proven areas and the drilling of wells for the purpose of extending the productive limits in producing fields constituted the bulk of development during 1940. Gaines County led all other counties in the district in the total number of oil-well completions. The oil production totaled 83,345,381 bbl., the highest figure for any year since proration was begun. The 1940 oil production exceeded the 1939 production by approximately four million barrels. Discoveries While comparatively few new oil-producing areas were discovered during 1940, it appears that the oil production found in simpson lime in the Abell field, pecos County, was an outstanding discovery for the year. This was the second Ordovician discovery in Pecos County. Taubert, McKee & Siemoneit located its discovery well, V. W. Crockett No. 1, set. 4 1/2 H. & T. C. R.R, co, survey in the Imperial area of northwestern Pecos County. The top of pay was encountered at 5270 ft., and the well was bottomed at 5357 ft. in simpson lime, on act. 17, I940. The initial production was 928 bbl. of 43" gravity sweet oil in 11 hr. 23 min., flowing naturally through 2-in. tubing with gas-oil ratio of 783 cu. ft. per barrel. Following the completion of the discovery well, large blocks of land were leased in the area, and several locations were made toward the close of the year. There is every indication that the Abell field will become a major producing field in the West Texas district. There was no pipe-line outlet for the field at the end of the year. Shipley-Silurian field, discovered by the Gulf Oil Corporation, appears to be another major addition to the oil reserves in 1940. The discovery well, Wristen Brothers No. 5, is in sec. 18, block 5, H. & T. C. R.R. Co. survey in Ward County. The well was drilled to a total depth of 9187 ft. and was plugged back to 7075 ft. The Silurian lime section was acidized with 3000 gal., from 6993 to 7075 ft., and on Dec. 5, 1940, the well was completed for initial production of 3040 bbl- of 32.2" gravity oil in 24 hr., flowing through tubing. Todd Deep field, Crockett County, was discovered by the Continental Oil Co. et al. The discovery well, J. S. Todd No. 2, set. 29, block WX1 G.C. & S.F. R.R. Co. survey, was completed on April 3, 1940. The top of pay was encountered at 5623 ft., and the well was bottomed at 5691 ft. for initial production of 1613 bbl. of 40.6&apos; gravity oil flowing naturally through 2-in. tubing. The pay section was found in Strawn lime of Pennsylvanian age. There were six producing wells in the field at the end of the year. This appears to be another major discovery in 1940. There was no pipe-line outlet in the field at the end of the

Jan 1, 1941

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.&apos; Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer&apos;s number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By P. P. Gregory

The rate of drilling operations in the West Texas district during 1940 was approximately equal to that of 1939. The total number of wells dillled in the area during the year was 1834, of which 1716 were completed as oil producers, 12 were gas wells and 106 were dry holes. The number of wildcat wells drilled during the year was comparatively small. The drilling of inside locations in proven areas and the drilling of wells for the purpose of extending the productive limits in producing fields constituted the bulk of development during 1940. Gaines County led all other counties in the district in the total number of oil-well completions. The oil production totaled 83,345,381 bbl., the highest figure for any year since proration was begun. The 1940 oil production exceeded the 1939 production by approximately four million barrels. Discoveries While comparatively few new oil-producing areas were discovered during 1940, it appears that the oil production found in simpson lime in the Abell field, pecos County, was an outstanding discovery for the year. This was the second Ordovician discovery in Pecos County. Taubert, McKee & Siemoneit located its discovery well, V. W. Crockett No. 1, set. 4 1/2 H. & T. C. R.R, co, survey in the Imperial area of northwestern Pecos County. The top of pay was encountered at 5270 ft., and the well was bottomed at 5357 ft. in simpson lime, on act. 17, I940. The initial production was 928 bbl. of 43" gravity sweet oil in 11 hr. 23 min., flowing naturally through 2-in. tubing with gas-oil ratio of 783 cu. ft. per barrel. Following the completion of the discovery well, large blocks of land were leased in the area, and several locations were made toward the close of the year. There is every indication that the Abell field will become a major producing field in the West Texas district. There was no pipe-line outlet for the field at the end of the year. Shipley-Silurian field, discovered by the Gulf Oil Corporation, appears to be another major addition to the oil reserves in 1940. The discovery well, Wristen Brothers No. 5, is in sec. 18, block 5, H. & T. C. R.R. Co. survey in Ward County. The well was drilled to a total depth of 9187 ft. and was plugged back to 7075 ft. The Silurian lime section was acidized with 3000 gal., from 6993 to 7075 ft., and on Dec. 5, 1940, the well was completed for initial production of 3040 bbl- of 32.2" gravity oil in 24 hr., flowing through tubing. Todd Deep field, Crockett County, was discovered by the Continental Oil Co. et al. The discovery well, J. S. Todd No. 2, set. 29, block WX1 G.C. & S.F. R.R. Co. survey, was completed on April 3, 1940. The top of pay was encountered at 5623 ft., and the well was bottomed at 5691 ft. for initial production of 1613 bbl. of 40.6&apos; gravity oil flowing naturally through 2-in. tubing. The pay section was found in Strawn lime of Pennsylvanian age. There were six producing wells in the field at the end of the year. This appears to be another major discovery in 1940. There was no pipe-line outlet in the field at the end of the

Jan 1, 1941

By E. H. Edwards, J. Washburn, E. R. Parker

The mechanism of strain hardening was discussed in connection with some recent observations on the stress-induced motion of dislocation boundaries and on the simple shear deformation of zinc, cadmium, and copper crystals. THE nature of work hardening accompanying plastic deformation of metals has long been the subject of speculation. As early as 1925, Becker&apos; suggested a thermodynamic process to explain slip based on the statistical probability for the occurrence of local glide steps. The theory that plastic glide was due to the presence of lattice defects known as dislocations was first introduced in 1934 by Taylor: and Orowan, and Polanyi.4 Taylor presented a rather complete analysis of the behavior and interaction of dislocations. He assumed a certain type of stress field to be associated with a single dislocation, and postulated that work hardening would result from plastic flow in two ways. First, dislocations following one another across a slip plane might encounter a barrier which would impede their movement, thereby gradually diminishing and eventually stopping plastic flow on that plane. The second mechanism involved the concept of dislocations traveling in opposite directions on nearby planes attracting one another to form a meta-stable lattice. The interaction of dislocations in such an array was shown to be large enough to require an increase in stress before plastic flow would continue. Kochendorfer5,6 extended the concept of work hardening involving a back stress due to an accumulation of like dislocations on a slip plane. He suggested that the formation of a new dislocation is hindered by those dislocations already present. The hardening resulting from the interaction of newly forming dislocations with bound dislocations was designated as "formative hardening," and indicated to be the only type of hardening necessarily connected with the slip process. In another detailed picture of work hardening, Mott and Nabarro7 assumed that sufficient dislocations are primarily present in the crystal as a consequence of growth irregularities (mosaic structure) to initiate slip. Work hardening resulted from the interaction of migrating dislocations with localized internal stresses produced during deformation. More recently, however, Mott8 as modified his treatment to include the generation of dislocations at Frank-Read sources and he accounts for the hardening by the formation of sessile dislocations. It has been widely accepted that metals of hexagonal structure, usually possessing only one set of glide planes, exhibit mechanical behavior markedly different from those having cubic structures. However, the differences in behavior of the two classes may be less fundamental than suggested. Rohm and Kochendorfer9 have shown that a single crystal of aluminum subjected to approximately simple shear gives the type of stress-strain curve associated with the hexagonal metals. Similar behavior has been demonstrated for gold and silver crystals by Andrade and Henderson.&apos;" Thus when glide in cubic metals is restricted to one plane, the strain hardening characteristics closely resemble those of the hexagonal metals. It would appear, therefore, that an investigation of some of the strain hardening properties of single crystals sheared in simple glide might provide a more complete understanding of the phenomenon of work hardening. This report relates a number of recent observations made on single crystals of copper, zinc, and cadmium tested in simple shear. In addition, pertinent observations of effects accompanying stress-induced movement of dislocation boundaries are reported. Experimental Procedure and Results Details of the production and advantages of the type of single-crystal shear specimen employed for the following tests have been presented in a previous publication.n The method of testing makes

Jan 1, 1954

By Adam L. Wesner, A. C. Richardson

DURING World War II the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pet iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pet of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The -10 +35 mesh fraction was found to be the most promising feed for producing the low-ash [ ] content coal. A batch of 30 tons of -3/8-in. coal was screened at 10 and 35 mesh; the yield of -10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the -35 +48 mesh range. A representative portion of the -10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pet ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1952

By J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse-grained high-purity aluminum at temperatures approaching the melting point permitted the formulation of a theory of subgrain formation. Subgrain boundaries were found to be formed by two different processes: kinking and polygonization. Polygonization is considered as the main factor in subgrain formation. SINCE "slipless flow" was first discussed in detail by Hanson and Wheeler,&apos; many studies have been undertaken to determine how metals deform at high temperatures. Several types of observations have been reported. Jenkins and Mellor,² working on the creep of mild steels and various grades of commercial irons, found metallographic evidence of a kind of substructure within the grains after deformation at high temperatures. Homes" observed after creep deformation of steel at high temperatures that the original X-ray spots were sharply divided into several small ones. The same phenomenon was reported by Hirst4 from his studies on lead and later by Crussard5 from his work on aluminum. The works of these investigators demonstrated beyond any doubt that the splitting of the X-ray spots was due to the fact that the grains underwent a division into subgrains during deformation at high temperatures. Since then, numerous experiments have been undertaken on aluminum in order to determine the mechanism of formation of subgrains. Research workers can be divided, for the purpose of discussion, into two different groups as regards thinking on subgrain formation. On one hand, based on the work on polygonization by Cahn,6 Guinier and Lacombe,7 Greenough and Smith," Crussard,10,11 and Servi, Norton, and Grant," it was concluded that subgrain formation was a consequence of the simultaneous effects, first, of inhomogeneous deformation which produced bending of the lattice, and second, polygonization. On the other hand, Wood and coworkers13-16 based their work on the results of an earlier report" which dealt with crystallite size and a fragmentation theory. It is interesting to note that while Greenough and Smith8 and Wood et al. performed similar experiments, their conclusions were quite different. Wood et al. did not recognize polygonization as a fundamental mechanism and said that aluminum, at the beginning of the deformation, fragmented immedi- ately into subgrains in order to permit deformation of the metal, the number of these subgrains being a function of strain rate and temperature. They concluded that deformation of grains occurred by flow along the subgrain boundaries. In view of the contradictory conclusions, it would appear that the data were not explicit enough to provide an unambiguous conclusion. It appears that the techniques by which most of the results were obtained, namely, X-ray work, were not enough by themselves to solve the problem. Another approach was needed. In the present research, therefore, an extensive metallographic study was planned to supplement the X-ray work. The importance of revealing the subgrain boundaries metallographically was realized, and this will explain the extensive development and use of etching techniques. In order that subgrains would be considerably larger and therefore more readily visible under a microscope, the creep experiments were performed at very high temperatures approaching the melting point of aluminum. Development of Experimental Technique Creep tests were run at constant load on high purity (99.995 pct) aluminum specimens having a very coarse grain size. None of the specimens was run to fracture. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled in the gage section to permit

Jan 1, 1954

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By Jerome F. Kuzmick

Many investigations have been made on the effect of the variables of pressure, sintering temperature and sintering time on the physical and microstructural charactcristics of metal-powder compacts. Severa1 such investigations have indicatcd that pressure is the least important of these three factors in an attempt to secure a dense. strong compact by a simple coltl-pressing and sintering procedure. However, it was felt that a further study of the effect of pressure on pressed and sintered metal powder compacts might prove interesting, for the following reasons: In work done in the past on the effect of pressure, temperature. arid time, the, metal-powder compacts were subjected to long sintering periods, and temperatures right up to the melting point of the metal were applied. It was thought that pressure might exert a more profound effect under short-time simtering and within narrower ranges of temperature. such as normally would be applied in large-scale production of metal-powder parts. 2. It was hoped that something further might be learned of the nature of the bond in pressed and sintered metal-powder compacts. 3. It was thought that interesting infor mation concerning the work-hardening effect of pressure on the crystal structure. of sintered metal-powder compacts would be obtained. Procedure Rectangular bars, 2 by 1/2 by 1/4 in. were molded from the following metal powders: Atomizcd till powder, 325-mesh Atomized aluminum powder, 325-mesh Reduced copper powder, 100-mesh Electrolytic iron powder, 100-mesh Atomized 70-30 brass powder, l00-mesh The, till powder was molded at various pressures up to 40 tolls per sq. in. This was the maximum, because at higher molding pressures there was considerable extrusion of tin into the die wall, jamming the die plungers. The tin specimens were not -in tered, as this phase of the work was- done merely to see how much a very sold metal could be compressed. The aluminum powder was compressed at various pressures up to 50 lons per sq in. Higher pressures could not be used because of extrusion into the die wall The compacts were sintered one hour at 000 in pure dry hydrogen. The copper powder was molded at vari-ous pressures up to 96 tons per sq. in. One set was sintered at 750°C., another at 050 C. for one hour in pure dry hydrogen. The electrolytic iron powder was molded at various pressures up to 00 tons per sq. in. and sintered, one set at Soo°C and one set at 1300°C for one hour in pure dry hydrogen. Extra 325-mesh specimens were also prepared to study the effect of reduced particle size on grain structure. The brass powder was molded at various pressures up to 96 tolls per sq. in. and silltered for one hour. one set at 65o°C. and one set at 800°C, in pure dry hydrogeu.

Jan 1, 1945

By W. C. Ellis

Growth directions of tin, zinc, and cadmiun whisker crystals grown spontaneously fi-om the solid are summarized. In tin the edge and diagonal directions of the unit cell are jound with the exception oj- the [110] diagonal. In cadmiurn and zinc the usual dip-ections are a or a + c. The c direction has not been ohserwed. The gvouth directions from the solid are for the most part the same as those found for vapor-grozun crystals and are the ohserz:ed glide directions in plastic j-lou. Whisker crystals of these elements grown from the solid are not twinned. Specular lateral reflections are associated with planes of snall crystallographic indices. WHISKER crystals of tin, zinc, or cadmium grow spontaneously at room temperature in periods from months to years from thin electroplates and other prepared films of the respective metals.&apos;&apos;2 It has been established that these crystals are single, but the question of twinning, such as occurs in whisker crystals of silicon,3&apos;4 has not been resolved. Studies of morphology have been restricted to determinations of growth directions.5-&apos; Whisker crystals are both straight and kinked. A few studies have been made on kinked whiskers including measurements of kink anglesa and determinations of growth directions,&apos; but unfortunately not both on the same crystals. The kink angles, for the most part, for each species are grouped closely about a few unique values, but these values are not always those between observed growth directions in a single crystal. To supplement existing data, the growth directions, identification of lateral features, and presence or absence of twinning were determined with a Weissenberg goniometer by a method described elsewhereg on eight whisker crystals of tin, five of zinc, and five of cadmium. One kinked cadmium whisker was examined in detail. The specimens were needlelike, a few microns in cross section, and of the order of a millimeter in length. They were removed from electroplated substrates on laboratory specimens and commercial equipment after several years of growth as described in Table I. Since the specimens were less than 10 p in cross section they were ideally strong with no attendant risk of plastic deformation or damage in handling. Only deformation twinning has been reported for these elements. Therefore, twinning probably should not be expected in whisker crystals of these metals, particularly a twin plane containing the growth direction. A twin plane oriented in this direction was the one sought in this study. No examination was made for twinning at the boundary between kink segments except for one cadmium crystal. Well-defined reflections occur as a whisker crystal of tin, zinc, or cadmium is rotated about its growth direction when illuminated by a beam of light Although these reflections had been noted in earlier investigations, no study of them was made, probably because the earlier studies had disclosed also that

Jan 1, 1967

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec&apos;, and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-&apos; Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10&apos;5 cm-sec&apos;1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys&apos; at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.&apos;, Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander&apos; and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.&apos; shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-&apos;. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By M. S. Burton, H. H. Kranzlein, G. V. Smith

The influence of up to 2 at. pct of Ni and Pt on the yield strength of mono- and polycrystalline high-purity iron has been evaluated at temperatures from + 25° to -196°C. Current theories of solid -solution strengthening fail to explain the experimental observations. The temperature dependence of yield stress was found to be less in the alloys than that in high-purity iron. The room-temperature yield stress increased with alloy content, but at —78°C the yield strength first decreased with increasing a1loy content. AS a result of many studies, a number of theories have been proposed for solid-solution strengthening. The purpose of the present study was to evaluate these theories, as applied to the solid-solution strengthening observed in Fe-Ni and Fe-Pt alloys. Of various theories of solid-solution strengthening, those of Cottrell,1,2 Fisher,3 Suzuki,4 and Mott and Nabarro5 are most prominent, and have been discussed widely in the literature.&apos;-&apos; Of the recent concepts of solid-solution hardening the work of Fleischer9 is notable. Each of these models has been applied to particular alloy systems with some success, but in general none has proved generally applicable. In many of the previous studies to assess the effects of alloy additions in ferrous systems, lack of adequate control of the purity and grain size of the materials has obscured strengthening effects, so that few comprehensive data relating composition, temperature, and change of lattice parameter have been determined. In the present investigation an attempt was made to obtain data which would be meaningful in evaluating the theories of strengthening. Materials of high purity were used to minimize extraneous impurity effects, and both single crystals and polycrystalline materials were studied to evaluate the effect of grain boundaries. Nickel and platinum were chosen as alloy additions, because both belong to the same chemical group and have the same crystal structure and valence, with markedly different atomic diameters. It appeared that some conclusions regarding atomic size effect on strengthening might be made. MATERIALS AND PROCEDURES Fe-Ni and Fe-Pt alloys containing 0.5, 1.0, 1.5, and 2.0 at. pct alloy additions were prepared from high-purity materials. The iron was supplied by the American Iron and Steel Institute from a stock of 99.98 pct zone-refined iron prepared by Battelle Memorial Institute. The minimum purity of the nickel and platinum used for alloying was 99.98 and 99.999 pct, respectively. Alloys were prepared by levitation melting, cast into cylindrical copper molds, and cooled, all under a partial pressure (0.3 atm) of purified helium. Samples were 0.375 in. in diameter and weighed 20 to 25 g. Chemical analyses of the alloys are given in Table I. A sample of unalloyed iron also was cast as a control specimen.

Jan 1, 1965

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts&apos; Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts&apos; Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman&apos;s recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts&apos; Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee&apos; to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By Falih Ergunalp

REGULAR production of chrome in Turkey started in 1860 with the operation of the Bursa deposits (5, Fig. I). Others were discovered at Makri, near Fethiye (3, Fig. I). For 33 years Turkey remained the principal source of this mineral. While new discoveries were coming in elsewhere, Turkey&apos;s output declined until 1921, as a result of four successive wars, which ruined the economics of the country. In 1927 a revival came with the production of 18,000 tons. In that year the Société Minière de Fethiye was formed. This company now operates mines in the Vilayets of Aydin, Denizli, Burdur and Mentese, and it has reached a maximum production of between 80,000 and 90,000 tons annually. The Turkish output therefore increased from 29,000 tons in 1930 to 55,000 tons in 1931; and to 119,009 tons in 1934. The second phase in the increase in chrome production in Turkey came about in 1935, when the Government decided to reorganize and control the mineral industry of the country according to the principles of "government control" of the present regime. Up to that time the mineral resources of the country had been exploited by private concerns. In 1935, the M.T.A. (Maden Tetkik ve Arama) Institute (Institute of Mining Research and Geological Survey) was established by the Government to do the geological and geophysical survey work and discover new mineral resources for the country. Before the establishment of the M.T.A. Institute, the chief chrome-producing region was Fethiye (3 and 4, Fig. I). As a result of the extensive work of this bureau, many new chrome deposits have been discovered and are now in production. The operational field of the mineral industry was given to Eti Bank, another Government-sponsored and Government-controlled establishment. Eti Bank gradually took over the exploitation of existing mines by purchasing them from privately operated companies. Attention was first given to the Zonguldak collieries and to the different chrome deposits scattered over the country. The Guleman mines (14, Fig. 1) were developed and put in operation in 1936. Since then the bulk of Turkish chrome output has come from this mine, which yields the highest grade ore in the world (averaging 52 per cent Cr2O3). In 1939, the recently discovered chrome deposits to the north of Eskisehir went into production, yielding ore having a Cr2O3 content of 51 to 52 per cent. Today, more than ever, the efforts of both the M.T.A. Institute and the Eti Bank are concentrated on finding new deposits and placing them in operation. There are still many promising regions of the country that merit systematic surveying and prospecting for chrome ores. Thus it is probable that Turkey will continue to make noteworthy progress in chrome output. As the annual chrome production of

Jan 1, 1944

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.&apos; This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.&apos;," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01&apos; the gas at the displacement front by evaporation of the C, - C,

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.&apos; This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",&apos; and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,&apos; and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,&apos; part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,&apos; in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,&apos; again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By G. L. Tufford, R. L. Bleifuss

Low-grade manganiferous iron ores of Minnesota&apos;s Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite with subsequent magnetic separation and flotation have not given satisfactory results because, in many instances, concentrate grade and manganese recovery are low. Metallization of iron and concurrent reduction of higher manganese oxides to MnO, as in the R-N process, followed by recovery of iron by magnetic separation and manganese by leaching, seems to be a technically feasible process. High-temperature x-ray diffraction studies show that solid-state reactions between iron and manganese, with the formation of intermediate iron-manganese oxides, occur during reduction and affect recovery of both iron and manganese from the final product. Solid state reactions also occur between FeO, MnO, and SiO, at temperatures as low as 900°C. The kinetics of these reactions are such that they become an important factor in the treatment of ores by the R-N process. These investigations suggest a temperature and gas composition cycle that would maximize both iron and manganese recovery. During the past ten years, iron ore shipments from the Cuyuna Range of Minnesota have decreased sharp1y. Because of adverse grade, structure, and cost, many Cuyuna ores are no longer competitive with high-grade foreign ores and domestic pellets. The low-grade manganiferous iron ores from the Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite for subsequent magnetic separation and flotation has not given satisfactory results because concentrate grade and manganese recovery are often low. However, a technically feasible process appears to be metallization of the iron and concurrent reduction of manganese oxides to MnO with recovery of metallic iron by magnetic separation and extraction of manganese from the tailings by leaching. In 1962 the R-N Corp., with a grant from the Area Redevelopment Administration, conducted an amenability study of the metallization of manganiferous iron ore from the Cuyuna Range. The results of this preliminary investigation were sufficient to interest the Economic Development Administration in sponsoring further studies of the process with emphasis on secondary recovery of manganese from the nonmagnetic tailings. Inasmuch as the metallization process has considerable influence on the final form of the manganese - its texture and distribution between the magnetic concentrate and nonmagnetic tailings-the investigation included a study of metallization of the ore as well. Therefore, the investigation conducted at the Mines Experiment Station covered three interrelated phases: (1) laboratory R-N roasting studies and magnetic separation tests, (2) laboratory chemical extraction experiments of the nonmagnetic tailings, and (3) a mineralogical study of the crude ores and their various roast products. High-temperature x-ray diffraction investigation of the Fe-Mn-Si0,-0, system is the main topic of this paper and an extension of the mineralogical work. GENERAL GEOLOGY The Cuyuna Range is known for its complicated geologic structure, complex orebodies, and generally indifferent response to attempts at conventional beneficiation. Several geologists have made intensive studies of the Cuyuna Range, including Leithl (1907), ~darns&apos; (1910), Zapffe3 (1925), Grout and Wolff4 (1955), and schmidt5 (1963), whose study was the most comprehensive of all. The Range is covered with glacial deposits - till, out-wash, and lake sediments -up to 250 ft thick. Bedrock stratigraphic units of the Cuyuna Range consist of three tightly folded Precambrian sedimentary formations. The lower unit is the Mahnomen formation, composed of 2000 or more feet of argillite, slate, siltstone, and quartzite. The middle unit is the Trommald formation, which varies from 45 to 500 ft in thickness and comprises the major iron-bearing formation. The upper unit is the Rabbit Lake formation, consisting of over 2000 it of argillite, slate, and interbedded lenses of lean iron formation. In the central part of the Cuyuna Range, the units have been folded into a series of

Jan 1, 1969

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey&apos; have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel&apos;perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,&apos; and Fletcher and Wilson&apos; have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971