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By W. S. Pellini, F. N. Rhines

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By Enid C. Plante, K. L. Sutherland

Practical metallurgists are unanimous in stating that oxidation of mined sulphide ore adversely affects separation of the constituent minerals under standard conditions in a mill. Frequently, the need for different operating conditions in different plants is attributed either to the extent of oxidation of the mineral surfaces or to soluble oxidation products. The investigations reported in this paper study the effect of oxidation on the primary condition necessary for flotation, namely that of adhesion of an air bubble to the mineral. Oxidation Products from Sulphide Minerals Weinig and Carpenter1 state that the relative rates of oxidation of some sulphides are: FeAsS > FeS2 > CuFeS2 > ZnS > pbS > Cu2S tetrahedrite. They also show that oxidation is rapid at first, that sulphides of older geological formations are more stable than those of recent date and that mixtures oxidize more rapidly than any one mineral alone. The more rapid oxidation of mixtures is borne out by results of Gottschalk and Buehler2 who found that PbS, zns and cus oxidized 8 to 20 times faster when pyrite was present. Only the end products of oxidation, sulphate and the metal ion, were identified in these tests. Gaudin3 states that pyrite is difficult to oxidize in the laboratory. Winchell,4 using pyrite containing 99.98 pct FeS2, allowed water to percolate through a bed of this ground material. At the end of three months only a trace of Fe+++and So4- were found. Even after 10 months the quantity of Fe+++ was only 7.8 mg and SO4- 25.5 mg per liter of percolating solution. Car-michael5 confirmed Winchell's results on the slow oxidation of pyrite. Usually the oxidation of sulphide surfaces has been conducted in neutral or acid solutions, the acidity being caused by the oxidation products. Eliseev and Nagir-nyaka found that treatment of pure pyrite with lime gave only thiosulphate, but considered it possible that thiosulphate was obtained not by oxidation of the pyrite itself, but by oxidation of calcium disul-hide. Mitrofanov7 suggested that thiO~ulphate was formed by the following process: oxidation of sulphide to give free sulphur (this frequently happens with marcasite), followed by oxidation of the sulphur to sulphur dioxide and reaction of the sulphur dioxide with sulphur to give thiosulphate. Ferric and ferrous hydroxides, or similar compounds, were shown to be present. The Research Staff of the United Verde Copper Co.8 treated ore from the United verde mine with lime. Thiosulphate, sulphide and polysulphides were stated to be

Jan 1, 1949

By Walter C. Holmes

IN the recently published book entitled "Man in a Chemical World," by A. Cressy Morrison, the several pages discussing explosives were included in the chapter on "Serving Industry." Such a classification is entirely correct, as blasting explosives function only as a tool for accomplishing certain useful work, a tool which is completely destroyed in one use. Explosives are so important to industry and to modern society, in fact, that it seems impossible to imagine the existence of civilized nations without access to commercial explosives as ready servants. Two main types of explosives are now in use, the low-velocity or deflagrating type, such as black powder, which is adapted for use in coal mining and other applications where a slow, heaving effect is desired, and high explosives of the dynamite type,

Jan 1, 1938

By Oliver Bowles

WHEN a new type of equipment revolutionizes methods of quarrying one kind of stone, producers of other kinds focus their attention on its potentialities in their particular fields. The purpose of this paper is to discuss the accomplishments of the wire saw in slate, to show its more limited attainments in other kinds of stone, and to point out the possibili-ties of much wider application. A wire saw consists of a 3/16-in. or 1/4-in. three-strand wire cable that runs as a belt and cuts the rock by abrasion. (Fig. 1.) The teeth of the saw are sand grains carried in the grooves between the strands.

Jan 1, 1936

By D. L., Hayes

THE concentration of zinc ore in Wisconsin is a comparatively simple process, although it presents problems that must be overcome in an efficient manner in such a way that installation and operating costs are low. As the ore deposits are small, the first cost of the concentrating plant must be low; while the low margin of profit makes it necessary to have the minimum operating costs. The original mills were copied from those of the Joplin district, as most of them were built and operated by Joplin millmen. These served the purpose well; they made a clean concentrate, which was the chief requirement at that time, as most 'of the mines were' considerably 'richer than the average at the present time, and wages and supplies were also considerably lower. ' The apparatus used at present has changed very little in principle. . The grizzly opening has gradually been increased to 12 in. and sometimes no grizzly 'is used. The crusher, gradually grew in size, the largest crusher has -an opening of about 24 by 13 in. and a 7/8-in. throw on the. eccentric shaft.

Jan 1, 1921

By E. L. Jr. Spain

THE deposits described in this paper occur over much of Wayne County and in the southeast portion of Hardin County, Tennessee, and in the northeast and northwest portions of Mississippi and Alabama respec-tively. The presence of tripoli in this region has been known for some time and descriptions of various occurrences in Tennessee have been made by Jewell1 and Miser2, while Hilgard3, Lowe4 and Logan5 have treated the deposits that occur in the adjacent portions of Alabama and Mississippi, but there has not been a general survey of the entire field summarizing completely the geology of the deposits with respect to their origin and stratigraphic relationships. During 1934, while engaged in surveys of mineral resources through this region for the Tennessee Valley Authority, the writer collected data with this in mind, and has assembled them in this report. He is indebted to H. S. Rankin and N. A. Rose, of the Tennessee Valley Authority Geology Division, for field assistance.

Jan 1, 1936

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz' to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""'"'"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15'F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By Robert H. Hafner, Irvin R. Kramer

IN recent years considerable interest has been shown in surface-alloyed metals, particularly those of chromium (chromized steels), which have excellent corrosion [ ] resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high temperatures of 1200° to 1400°C. (2200° to 2550°°F,) caused excessive grain growth and warpage, Louenstein and Ulmer2 packed iron castings in ferrochromium and com- [ ] mon salt, and heated for approximately three hours at 930° to 1040°C. (1700° to 1900°F,). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900° to 1000°C., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a chromized layer, 0.004 in, thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1942

By Robert H. Hafner, Irvin R. Kramer

IN recent years considerable interest has been shown in surface-alloyed metals, particularly those of chromium (chromized steels), which have excellent corrosion [ ] resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method' employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high temperatures of 1200° to 1400°C. (2200° to 2550 F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- [ ] mon salt, and heated for approximately three hours at 930° to 1040°C. (1700° to 1900°F.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900° to 1000°C., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1942

By H. A. Doerner

PROPOSALS to use hydrocarbon or natural gases for the reduction of zinc from oxide materials may be traced back through Patent Office files to the early years of the present century. Natural gas at rates cheap enough to compete with solid fuels has been available at or near one major zinc district for more than a decade. That the seemingly meritorious and economically interesting applications of these proposals have not devel-oped into workable processes for direct production of zinc by natural gas cannot be completely ascribed to the proverbial conservatism of the zinc industry. It is possible to produce spelter commercially in normal times from zinc oxide and carbonaceous reducing agents without having a very precise understanding of the chemistry of the process. The reduc-tion by hydrocarbons is not, however, in this class, and the technical complexity of this reduction metallurgy and chemistry prohibits solution of the inherent difficulties by the "hit and miss" methods that are some-times thought to be practical. In a thermodynamic study of the chemistry of zinc smelting, Maier1 made a preliminary study of the chemistry of the use of methane for reducing zinc oxide by thermodynamic means, pointing out that the following reactions, the limits of which could be theoretically predicted, were important: ZnO + CH4 = Zn(gas) + CO + 2H2 [1] CH4 = C -I- 2H2 [2] ZnO + CO = Zn(gas) + CO2 [3] ZnO + H2 = Zn(gas) + H2O [4] Other possible reactions, not discussed in the reference quoted, are: CO2 + CH4 = 2CO + 2H2 [5] H2O + CH4 = CO + 3H2 [6]

Jan 1, 1933

WHILE papers on cleaning coal and mining coal were presented at the iron and steel and mining methods sessions, respectively, the first general session on coal was held on Wednesday afternoon. Howard Eavenson of Pittsburgh, Pa., as chairman of the session,* reported progress by the Committee on the Valuation of Coal for Blast-Furnace Coke. A paper on blasting coal effectively and safely in Southern Illinois, by J. E. Tiffany and S. S. Lubelsky, was abstracted and commented on by Dan Harrington, of the U. S. Bureau of Mines. W. J. German commented on some conditions mentioned in the paper as unsafe or bad practices, and added to these some further ex-amples; he made a strong plea for holes to be: drilled parallel to the bedding as the easiest way to determine the proper length or depth to agree, with the depth of kerf cut. Mr. Barron called attention to proper cutting and-drilling and rate of detonation of the explosive used, as effective aids in blasting coal. Another speaker mentioned an odd case where compressed black powder or "pellet powder," had decreased accidents at a non-gaseous mine where permissible explosives had been formerly used; the permissible cracked or shattered the roof, with a resulting high accident rate from falls of roof, and pellet black powder overcame this trouble. Eugene McAuliffe of the Union Pacific Coal Co. told of difficulties in changing from black powder to permissible in Wyoming mines. J. B. Dilworth read a paper on valuation of coal prop-erties, expressing a preference for the method of capi-talizing the earning power of a property. Eli T. Con-ner of Scranton, Pa., with much experience in valuation work, stated that the method was undoubtedly good, but many times failed because of inability to forecast accurately future earnings, and further contended that total valuation -and royalty rates could generally be fixed fairly when based on similar neighboring proper-ties' rates when these had recently been established by a free bargaining. S. A. Taylor of Pittsburgh, Pa., stated that a leasehold value could be fairly established by figuring based on 10 to 20 per cent of the profit resulting from operation. The chairman read a written discussion from Henry Louis of England, called atten-tion to differences in valuation resulting from whether gross or net profit or earnings were used as a basis for capitalizing. John A. Garcia of Allen & Garcia gave a most inter-esting account of coal mining and general conditions in Russia as noted in his recent extensive visit there, which appears elsewhere in this issue. Although agree-ing with most thinking Americans that government operation is incompatible with progress, he showed that mining conditions were far from impossible in present-day Russia. Charles E. Stuart gave motion pictures of parts of the trip, with, his own comments supple-menting those of Mr. Garcia.

Jan 3, 1928

By Albert Sauveur

To understand this paper properly, the reader must have a clear conception of what is meant by the " critical points " of iron and steel; * and in order to avoid the necessity of tedious references to previous publications on the part of those unfamiliar with the subject, it is here briefly recapitulated. Critictl Points.—If a piece of steel containing, say, 0.50 per cent. or more of carbon, be heated to a high temperature and then allowed to cool slowly, the cooling proceeds at first at a uniformly retarded rate until a temperature of about 700° C. is reached, when there is a sudden " retardation " in the fall of

Jan 1, 1897

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By J. N. Breston, R. V. Hughes

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20's before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By R. V. Hughes, J. N. Breston

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20's before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By J. B. Bassett, E. S. Rowland

The experimental work reported herein firas inspired by the publication of a paper by Grange and stewart, in which it was suggested that at low chromium contents the effect of this element on the Ma point was greater than at higher chromium contents, It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the M, point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature, such enrichment of the austenite in chromium content would lower the M, point nearer room temperature where cracking is more likely to occur. According, it was decided to investigate the effect of chromium, in quantities between o and 2 pet, on the M, point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the M, temperature values were corrected by means of the Grange and Stewart formulas to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (z) Hsereutectoid compos-sition': 1." pet carbon and O.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased error such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question Of the effect Of chromium On the Md Oint, particularly at low chromium contents. While it is fairly well established that chromium causes the M, to be lowered when present in quantities of I pet Or more, Grange and Stewart1 have suggested that in small amounts (less than 1 pet) it is more effective in lowering the Ma point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the Ma point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the Ma point of a 0.20 carbon steel. Material Two series of 35 Ib induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0,25 pet increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1949

By F. P. Haver, M. M. Wong

When a mixture of chalcopyrite concentrate and lime is heated in air, the following reaction takes place: 2CuFeS2 + 4Ca (OH)2 + 8 ½ 02 ; 2Cu0 + Fe203 + 4CaS04 + 4H20. Ca (OH)2 is the only common reagent that will adequately control SO2 evolution in roasting. Other additives tried, including CaO, CaCO3, Na2CO3, NaOH, MgO, Mg (OH)2, and MgCO3, were not effective. All reacted with sulfur, but not to the extent that will be required to meet the new control regulations for sulfur oxide emissions. For example: when the concentrate was heated with the theoretical amount of limestone (CaCO3), about 55% of the sulfur was retained in the calcine; whereas use of the stoichiometric amount of Ca (OH), converted approximately 99% of the sulfur to CaSO1. In most of the experiments, Ca(OH)2 was formed by adding CaO to concentrates containing enough water to simulate filter cake from flotation circuit. This eliminated the need for drying the concentrate and utilized the heat of hydration of CaO.

Jan 6, 1972

By Paul M. Tyler

MINOR industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz (Iceland spar, tourmaline, fluorite, selenite, mica), and nonfuel gases (air, helium, carbon dioxide). ALUM MINERALS The alums comprise a series of double sulphates (or selenates) isomorphous with potash alum, which, according to a ruling of the Pennsylvania courts, is the only product commercially described simply as "alum." Common alum occurs in nature as kalinite (K2SO4- A12 (SO4) 324H2O). The mineral mendozite (Na2S04) 3.A12 (SO4)3- 24H2O) is soda alum; tschennigite (NH4)2SO4.Al2 (SO4)3.24H2O) is ammonium alum; and there are about a dozen other native alums and related double sulphates. Alunite (alumstone or alum rock) has the formula Al2(SO4) 3.K2S04.4A1 (OH)3 and alunogen, Al2(So4) 3.18H20. Saline residues, found wherever natural water is evaporated, may contain sulphate of alumina, which for most uses is the essential ingredient of alum. Mineral wells and springs that emerge from beds of pyritiferous shale are typically astringent and at times form local deposits of alum, generally as incrustations. Acid waters acting upon aluminous rocks may form sulphates of alumina. The alums of commerce, as well as aluminum sulphate (concentrated alum), are produced principally by treating bauxite with acid, but they have been made also on a substantial scale from clay, cryolite, pyritic slates, schists, lignites, alunite, and leucite. Alum shale-chiefly clay, pyrite, and (usually) carbonaceous matter-was extensively used in England as a source of alum for more than two centuries. In France, pyritic lignites mixed with sand and clay were burned in heaps to red ash, the leach Liquors from which, after treatment with ammonia, yielded alum and copperas. Processes have been developed for making alum or aluminum sulphate from such diverse materials as feldspar, aluminous phosphate minerals, greensand, and mixtures of mica and

Jan 1, 1949

AGGLOMERATION U.S. 4,067,727 - In the sintering of a charge of iron oxide ore, a fuel and a flux on a travelling grate machine, the dust problem is minimized by providing a plurality of cooling zones and by directing heated dust-laden air from a first cooling zone to the sintering zone wherein the dust is filtered from the air by the material being sintered. Air from a further cooling zone can be exhausted directly to the atmosphere. Dust removal in the cooling zone is improved by using a purging zone in which higher pressure air agitates the dust in the sintered material. This patent is a division of U.S. Patent No. 3,973,762, dated Aug. 10, 1976. F. Cappel, assigned to Dravo Corp. Jan. 10, 1978. 6 pp. (75-5). Filed: 4-1-76 (672,748).

Jan 1, 1979

By G. K. Manning, A. R. Elsea, A. B. Westerman

A considerable number of high-tem-perature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. .4t the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in vitalliurn after various heat treatments. Howcver, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chro-mium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja and Guertler2 indicated that cobalt and chro-mium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to 85 pct chromium undergo a transformation at [zoo to 12 50 c More recently, Wever and Haschimoto,3 Wever andLange,4and Matsunaga5 carried Out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallogra~hic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Mat-SUnaRa. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these excep-tions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data arid the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitalhum by deter-mining the diagram for the cobalt-chro-mi~m system- Experimental Work For the convenience Of the reader, the diagram as determined by the present investigation is presented in Fig 3. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the melting point for pure chromium is the

Jan 1, 1949