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By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult's law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa's4 data, and Kubaschewski7 has similarly treated Kawakami's7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By S. D. Michaelson, Eric Sinkinson

Many of the magnesite ores of the western part of the United States contain such large amounts of silica and hydrous silicate minerals that the value of the ores is either low or nominal. Expensive and carefully controlled mining methods are necessary to prevent excessive dilution of the higher grade ores by introduction in mining of small pieces of the hanging walls or footwalls of the deposit. This difficulty is further complicated by the various states of decomposition of the country rock of the deposits in which many of the ores occur. The problem the authors attempted to solve arose from a request to float an impure magnesite containing varying proportions of siliceous gangue with calcium carbonate. The ore is normally enclosed in serpentine masses, somewhat decomposed, and in mining it wall rock is incidentally added, so that variable amounts of siliceous material occur in the samples. The silica, alumina, and iron oxide are so closely associated with the magnesium carbonate in the magnesite that ordinary mechanical separation at coarse mesh sizes is of no avail. It is well known that calcium carbonate can be floated by suitable reagents, therefore it seemed reasonable to suppose that magnesium carbonate minerals would behave in a similar manner, but experimental trial proved that this supposition was unfounded. Therefore the first step in the problem was to find out what differences of behavior there were between magnesium and calcium carbonates under flotation conditions, or when suspended in water. In water at 18" C. magnesium carbonate is slightly more soluble than calcium carbonate; in fact, MgCO3 is soluble to the extent of 0.0106 grams in 100 c.c. of water at 18" C. and CaCO3 to the extent of 0.0013 grams. However, magnesium carbonate in water gradually changes to the basic carbonates of a composition (3MgCO3.Mg(OH)23H2O) or (4MgCO3.Mg(OH)25H2O), depending upon conditions, and calcium carbonate to calcium hydroxide, Ca(OH)2. The relative solubilities of these hydroxides in water are the reverse of the solubilities of magnesium and calcium carbonates. The range in published figures for solubility

Jan 1, 1938

By S. D. Michaelson, Eric Sinkinson

Many of the magnesite ores of the western part of the United States contain such large amounts of silica and hydrous silicate minerals that the value of the ores is either low or nominal. Expensive and carefully controlled mining methods are necessary to prevent excessive dilution of the higher grade ores by introduction in mining of small pieces of the hanging walls or footwalls of the deposit. This difficulty is further complicated by the various states of decomposition of the country rock of the deposits in which many of the ores occur. The problem the authors attempted to solve arose from a request to float an impure magnesite containing varying proportions of siliceous gangue with calcium carbonate. The ore is normally enclosed in serpentine masses, somewhat decomposed, and in mining it wall rock is incidentally added, so that variable amounts of siliceous material occur in the samples. The silica, alumina, and iron oxide are so closely associated with the magnesium carbonate in the magnesite that ordinary mechanical separation at coarse mesh sizes is of no avail. It is well known that calcium carbonate can be floated by suitable reagents, therefore it seemed reasonable to suppose that magnesium carbonate minerals would behave in a similar manner, but experimental trial proved that this supposition was unfounded. Therefore the first step in the problem was to find out what differences of behavior there were between magnesium and calcium carbonates under flotation conditions, or when suspended in water. In water at 18" C. magnesium carbonate is slightly more soluble than calcium carbonate; in fact, MgCO3 is soluble to the extent of 0.0106 grams in 100 c.c. of water at 18" C. and CaCO3 to the extent of 0.0013 grams. However, magnesium carbonate in water gradually changes to the basic carbonates of a composition (3MgCO3.Mg(OH)23H2O) or (4MgCO3.Mg(OH)25H2O), depending upon conditions, and calcium carbonate to calcium hydroxide, Ca(OH)2. The relative solubilities of these hydroxides in water are the reverse of the solubilities of magnesium and calcium carbonates. The range in published figures for solubility

Jan 1, 1938

By Howard Smith

AT the meeting of this Institute in February 1933, I presented a paper on potash development in southeastern New Mexico1, which contained a brief review of the Geological Survey's 20-year search for commercial sources of soluble potash minerals and of the events, that led to the discovery, exploration, and first development of the deposits in that state. As a more comprehensive review of the subject was published in December2, the present paper is intended only to discuss recent developments in the domestic potash industry, particularly in New Mexico. A summary of the findings of potash in the Permian Basin, by. G: R. Mansfield and W. B. Lang, geologists of the United States Geological Survey, is now in process of publication by the University of Texas and will be omitted from this paper. In New Mexico prospecting for potassium salts during the past two years has increased materially the known area .of commercial deposits; development has resulted in an increase from one to three in the number of shafts and the starting of a fourth; an increase of annual productive capacity to 1,000,000 tons of crude salts, or 250,000 tons of K20; and an increase in annual refining capacity to 140,000 tons of muriate of 62.5 per cent grade. Construction has been completed to increase still further the production of high-grade salts. In California the American Potash & Chemical Co., operating on Searles Lake brines, has increased its plant capacity from about 100,000 tons to 180,000 tons of muriate a year and is now producing soda ash and salt cake in addition to potash and borax. Potash production from cement-plant and industrial-alcohol wastes remains unimportant.

Jan 1, 1935

By Howard J. Smith

At the meeting of this Institute in February 1933,I presented a paper on potash development in southeastern New Mexico1, which contained a brief review of the Geological Survey's 20-year search for commercial sources of soluble potash minerals and of the events that led to the discovery, exploration, and first development of the deposits in that state. AS a more comprehensive review of the subject was published in December2, the present paper is intended only to discuss recent developments in the domestic potash industry, particularly in New Mexico. A summary of the findings of potash in the Permian Basin, by G. R. Mansfield and W. B. Lang, geologists of the United States Geological Survey, is now in process of publication by the University of Texas and will be omitted from this paper. In New Mexico prospecting for potassium salts during the past two years has increased materially the known area of commercial deposits; development has resulted in an increase from one to three in the number of shafts and the starting of a fourth; an increase of annual productive capacity to 1,000,000 tons of crude salts, or 250,000 tons of K2O; and an increase in annual refining capacity to 140,000 tons of muriate of 62.5 per cent grade. Construction has been completed to increase still further the production of high-grade salts. In California the American Potash & Chemical Co., operating on Searles Lake brines, has increased its plant capacity from about 100,000 tons to 180,000 tons of muriate a year and is now producing soda ash and salt cake in addition to potash and borax. Potash production from cement-plant and industrial-alcohol wastes remains unimportant.

Jan 1, 1938

By Howard J. Smith

At the meeting of this Institute in February 1933,I presented a paper on potash development in southeastern New Mexico1, which contained a brief review of the Geological Survey's 20-year search for commercial sources of soluble potash minerals and of the events that led to the discovery, exploration, and first development of the deposits in that state. AS a more comprehensive review of the subject was published in December2, the present paper is intended only to discuss recent developments in the domestic potash industry, particularly in New Mexico. A summary of the findings of potash in the Permian Basin, by G. R. Mansfield and W. B. Lang, geologists of the United States Geological Survey, is now in process of publication by the University of Texas and will be omitted from this paper. In New Mexico prospecting for potassium salts during the past two years has increased materially the known area of commercial deposits; development has resulted in an increase from one to three in the number of shafts and the starting of a fourth; an increase of annual productive capacity to 1,000,000 tons of crude salts, or 250,000 tons of K2O; and an increase in annual refining capacity to 140,000 tons of muriate of 62.5 per cent grade. Construction has been completed to increase still further the production of high-grade salts. In California the American Potash & Chemical Co., operating on Searles Lake brines, has increased its plant capacity from about 100,000 tons to 180,000 tons of muriate a year and is now producing soda ash and salt cake in addition to potash and borax. Potash production from cement-plant and industrial-alcohol wastes remains unimportant.

Jan 1, 1938

By Kennedy, Joseph E.

MANY things must be considered in coming to a decision as to what type of crushing and grinding equipment is to be used for preparing run-of-mine ore for concentration, amalgamation, flotation, or cyanidation. This paper is intended in no sense as a thorough discussion of these various factors, but rather contains a few observations based on a wide experience in the manufacture and application of milling machinery. One important governing factor is the tonnage to be dealt with. In large plants treating several thousands of tons in eight hours, a large jaw or gyratory crusher of substantial construction is standard equipment for reducing ore to 8 or 10 in. or finer. In open-pit work, using power shovels with 4- or 5-yd. dippers, a jaw crusher should have a receiving opening of 48 by 60 in., or 60 by 84 in., so that dynamite or hand sledging will not be required for breaking to a finer size before primary crushing. The coarsely broken ore is then conveyed by a belt to vibrating screens, the oversize from which is again conveyed by belts to secondary crushers having openings of 12 or 14 in., the product from which is conveyed to storage. From storage, the material goes to a finishing gyratory for reduction to 1/4 in. or finer.

Jan 1, 1936

By Oliver C. Ralston

A definite field of usefulness has developed for the brine-leaching processes of removing lead from ores and other products, so this paper reviews the developments, both in practice and in research, that have taken place since the publication of two earlier papers on this subject.' Several commercial plants are now in operation and a number of semi-commercial test plants have been operated in an effort to determine the limitations of brine leaching and to compare the results with other forms of treatment. Briefly, the brine leaching of lead depends on the fact that lead chloride and lead sulfate are soluble in saturated sodium-chloride solutions. In dilute brines, the solubility of the lead salt is less than in pure water; but in the strong brines, the solubility is greater than in pure water due, supposedly, to the formation of a double sodium-lead chloride. This is seen in Fig. 1, which shows the results of M. Demassieux2 on the solubility of lead chloride in sodium-chloride solutions of different concentrations and at three temperatures. The curves are not those given by Demassieux but are calculated from his results in order to convert them to units common in metallurgical work. The right-hand branch of each curve shows that if the solution is kept in contact with solid sodium chloride the lead chloride can be almost entirely displaced from solution, but that brines which are saturated with sodium chloride, but are not in contact with the solid salt, have a very high solubility for lead chloride. The diagram gives the analysis of the solution in grams of lead per liter, although the substance actually in solution is lead chloride. At 100" C. as much as 100 gm. of lead per liter can be obtained; but at lower tem-

Jan 1, 1924

W. H. LINNEY, Chairman, OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154; Spokane, Wash. STANLY A. EASTON, S. SHEDD. Mining camps from Mexico to Alaska and from the Pacific coast to the Atlantic were represented by delegates at the 5th Annual Northwest Mining Convention which was held in Spokane, Wash., Feb. 19-24, 1917. About 300 delegates from outlying regions were present, this being fully 100 more than have been counted at any previous mining convention in Spokane. Graham B. Dennis, president of the Northwest Mining Association, made the address of welcome. In part, he said: "Heaven has made us the possessors of an area great enough for an empire, varied enough in climate and possibilities to compass the whole complex field of modern industry. In the development of this broad heritage, we are not only actors for today, but trustees for future ages. "It is to foster this spirit of unity; to create and maintain strong bonds of mutual good will and confidence, that we founded the Northwest Mining Association. Wee support it because we believe it will give us strength; because we believe we shall learn from each other; because, in industry as in every other walk of life, personal contact and establishment of ties of friendship enrich and round out the characters of men." One of the interesting lectures of the week was that on "Alaskan and Russian Gravel Mining," by Dr.' Henry Mace Payne, consulting engineer for the Russian government and Consolidated Goldfields of South Africa. Dr. Payne's illustrations showed the different appliances in use in the countries mentioned. The Resolutions Committee reported back to the Convention six of the seven resolutions that had been presented to it. These were adopted as submitted, with some minor changes.

Jan 5, 1917

By Y. Nakada, E. J. Fasiska, A. S. Keh, L. Zwell

DURING an investigation of solid-solution hardening of nickel by carbon,' we found that there were no reliable data on the dilating effect of dissolved carbon on the unit cell of nickel. Bernier2 reported an increase in lattice parameter of nickel (3.523A) when an unknown amount of carbon was introduced into solid solution (3.536A). Similarly KG, Tsien, and Misek3 found an increase from 3.523 to 3.531A when nickel was carburized. strong4 studied the variation of nickel lattice constant as a function of dissolved carbon. However, in his case carbon was introduced into nickel by solidifying the melt at 65 kbar. Therefore, his carbon concentrations were much above the highest equilibrium solubility limit5 (2.7 at. pct C at 1 atm). Knowledge of the lattice mismatch between solute and solvent is essential in understanding the mechanism of solid-solution hardening. Therefore, we decided to determine the dilation of the nickel lattice by carbon under the more usual conditions of atmospheric pressure. The material used was Inco Electrolytic Nickel of 99.95 pct purity, as specified by the supplier. The impurity contents in wt pct were: Fe, 0.01; Cu, 0.01; Co, 0.03; 0, 0.005; C, Si, S, N, trace. To this base material various amounts of AUC-grade high-purity carbon were added during vacuum induction casting. Ingots, 2 in. in diam, were heated in a muffle furnace at 1000°C for i hr., hot-rolled to 1/2-in. thickness, and quenched into brine. All ingots with carbon concentration greater than 0.98 at. pct were enclosed in a cast iron box during the heating to minimize decar-burization. Small pieces were then either swaged down to 0.028-in.-diam wire or cold-rolled to 0.010-in.-thick sheets. After the final cold reduction in area of 50 pct, the specimens were recrystallized by heating in evacuated capsules at 1100°C for 60 to 80 sec and then quenched into brine. The final grain size was 50 to 100 µ. The carbon contents of the alloys, Table I, were determined by a combustion method

Jan 1, 1969

By Rollin E. Hook, Attwell M. Adair

The response of CrzO3 and C~304 to various heat treatments was studied in are-melted iodide chromizim over the temperature range 1000" to 1750°C. These oxides, which are present as impurity phases in this material, were identified by X-ray diffraction teclzniques which were supplemented by optical metallop-aphy. As a function of increasing temperature, Crs04 is first observable in samples annealed at 1300°C and coexists with Cr2O3 (the low-temperature oxide) over a temperature range exceeding 200°C. As the temperature decreases, Cr3O4 dissolves with the concomitant precipttation of Cr2Y2. Both oxides precipitate predominantly at pain boundaries. The reactions which occur are involved with at least ternary equilibria, possibly due to iron which is present as an impurity in arc-melted iodide chromium. HILTY, Forgeng, and Folkman' reported in their investigation of the Fe-Cr-0 system that Cr3O4 (with about 8 pct Fe substituted for chromium) is a primary phase found in alloys with 9 or more pct Cr. They reported that this phase is stable only at high temperatures and that below the liquidus Cr3O4 is disproportionated into Cr2O3 and chromium-rich metal for both Fe-Cr-O alloys and in oxygen saturated pure chromium. Further, they proposed that CrsO4 forms by a peritectic reaction between Cr2O3 and the liquid. On the other hand, Hook, Garrett, and Adair2 found in their investigation of impurity phases formed in "pure" chromium (material consolidated from iodide chromium crystals) that Cr3O4 forms intergranularly and is stable as low as 1500°C which is 375OC below the melting point of chromium. The purpose of the research described herein is to determine the temperature range of stability of Cr3O4, and to show the nature of its decomposition. This further investigation indicates that Cr3O4 undoubtedly occurs in this material as low as 1300°C. The chromium studied was consolidated and fabricated from iodide chromium crystals (ICr-5) and contained Fe r 135 ppm, Si = 20 to 100 ppm, and 0 = 35 to 137 ppm. A complete chemical analysis is given elsewhere.' Annealing was conducted in 1 atm of purified helium and all samples were rapidly cooled (-200°C per sec) by withdrawing them from the furnace hot zone under a high flow rate of helium. The details of the electrolytic-etching technique and electrolytic-digestion techniques for preparation of insoluble residues for X-ray examination are given elsewhere also.' EXPERIMENTAL RESULTS The Starting Material. The as-swaged rod (final swaging done at 900°C) had a wrought grain structure and contained a dispersion of CrzO3 inclusions of maximum particle size of about 2 or 3 p, Fig. 1. The microstructure also contained a dispersed

Jan 1, 1964

By L. E. Shiffman

W. J. Parton—Those operators faced with the problem of treating fine coal whether in bituminous or anthracite will find this paper most timely. I would like to take this opportunity of discussing Mr. Schiffman's paper and at the same time express certain views relating to our Tamaqua plant. I would like to ask the author what type of impeller and diffuser is used in the Denver cells? Screen analysis of products from individual cells indicate that coarser material resists flotation and only floats after greater retention time in the last few cells. Also, the need for a scavenger screen to reclaim non-floated coal particles further stresses this point. I have always felt that more efficient means of cleaning coal between 10-mesh and 28-mesh existed than flotation. Reagent and power costs are high for the flotation process. When floating +28-mesh particles, cell capacity is lowered and some of the particles are lost with the refuse. The Tamaqua plant of the Lehigh Navigation Coal Co. floats —28-mesh coal and capacity of recoverable coal is 40 tph for 1800 cu ft of Denver cells; or 0.05 tons per cu ft of cell. At Kimberly 7.75 tph for 600 cu ft of cell gives 0.013 ton per cu ft of cell. At Bessie 14 tph for 800 cu ft of cell gives 0.017 tons per cu ft of cell. It would be appreciated if the author would comment on what he feels is the upper size limit of particle to attain most efficient utilization of the flotation process. The dewatering screw is a very interesting development since it offers a simple way to prepare coal sludge for more complete clewatering by drainage or mechanical dewatering on screen or filters. In other words it could be used to accomplish the same thing as a thickener tank. I would appreciate having the author's comment on how he thinks such a screw dewaterer would work on a froth.* The process as used in floating coal at the Bessie and Kimberly plants may be referred to as more of a bulk oil float in contrast to a froth flotation process. Experiments on increasing capacity of cells is most interesting since we are going through such an experi- mental period at the present time. Recently a double overflow was installed on our No. 30 Denver cells. So far results are not conclusive. In reviewing this paper the following comments are made pertaining to investigation of methods for increasing capacity: Supercharging: Supercharged air in matte flotation or for that matter the use of the normal amount of air drawn in by the impeller would in all probability cause such an aeration in the cell as to destroy the buoyant effect given to the coal particles by the excessive amount of kerosine used. In other words, air creates an agitation zone throughout the cell, creating a boiling and thereby giving a lower recovery in the cell. It would be interesting to know whether the 7 pct increase in recovery was with no air being admitted to the stand pipe. Changing Impeller Speed: The speed of a receded disc impeller for a No. 30 cell as recommended by the Denver Equipment Co. is, I believe, approximately 250 rpm. At this speed and using supercharged air in excess of 8-oz pressure, we have observed a boiling action in the cells. In our flotation we endeavor to obtain some degree of froth flotation using pine oil as a frother. The boiling action as caused by increasing the amount of air added to the cells is detrimental to recovery in froth flotation. It is our belief that to obtain increased recovery from a cell in froth flotation, additional air must be introduced but at the same time this air must be dispersed throughout the pulp in the form of small bubbles and this can only be done by increasing the speed of the impeller. Therefore, if Mr. Schiffman decreased the speed of the No. 30 impellers and at the same time continued to use supercharged air, the boiling action may have been increased because larger bubbles developed. The lower recovery as reported could be due to this factor. Decreasing the impeller speed will definitely decrease the power consumed but may have other disadvantages. First, we believe it will permit "sanding" in the cell and this in our opinion will increase the wear on the impeller and diffuser, especially so, if there is pyrite and/or sand present in the feed. "Sanding" in the cell when air is used, as in froth flotation, will effect the dispersion of this air and cause boiling.

Jan 1, 1951

By L. E. Shiffman

W. J. Parton—Those operators faced with the problem of treating fine coal whether in bituminous or anthracite will find this paper most timely. I would like to take this opportunity of discussing Mr. Schiffman's paper and at the same time express certain views relating to our Tamaqua plant. I would like to ask the author what type of impeller and diffuser is used in the Denver cells? Screen analysis of products from individual cells indicate that coarser material resists flotation and only floats after greater retention time in the last few cells. Also, the need for a scavenger screen to reclaim non-floated coal particles further stresses this point. I have always felt that more efficient means of cleaning coal between 10-mesh and 28-mesh existed than flotation. Reagent and power costs are high for the flotation process. When floating +28-mesh particles, cell capacity is lowered and some of the particles are lost with the refuse. The Tamaqua plant of the Lehigh Navigation Coal Co. floats —28-mesh coal and capacity of recoverable coal is 40 tph for 1800 cu ft of Denver cells; or 0.05 tons per cu ft of cell. At Kimberly 7.75 tph for 600 cu ft of cell gives 0.013 ton per cu ft of cell. At Bessie 14 tph for 800 cu ft of cell gives 0.017 tons per cu ft of cell. It would be appreciated if the author would comment on what he feels is the upper size limit of particle to attain most efficient utilization of the flotation process. The dewatering screw is a very interesting development since it offers a simple way to prepare coal sludge for more complete clewatering by drainage or mechanical dewatering on screen or filters. In other words it could be used to accomplish the same thing as a thickener tank. I would appreciate having the author's comment on how he thinks such a screw dewaterer would work on a froth.* The process as used in floating coal at the Bessie and Kimberly plants may be referred to as more of a bulk oil float in contrast to a froth flotation process. Experiments on increasing capacity of cells is most interesting since we are going through such an experi- mental period at the present time. Recently a double overflow was installed on our No. 30 Denver cells. So far results are not conclusive. In reviewing this paper the following comments are made pertaining to investigation of methods for increasing capacity: Supercharging: Supercharged air in matte flotation or for that matter the use of the normal amount of air drawn in by the impeller would in all probability cause such an aeration in the cell as to destroy the buoyant effect given to the coal particles by the excessive amount of kerosine used. In other words, air creates an agitation zone throughout the cell, creating a boiling and thereby giving a lower recovery in the cell. It would be interesting to know whether the 7 pct increase in recovery was with no air being admitted to the stand pipe. Changing Impeller Speed: The speed of a receded disc impeller for a No. 30 cell as recommended by the Denver Equipment Co. is, I believe, approximately 250 rpm. At this speed and using supercharged air in excess of 8-oz pressure, we have observed a boiling action in the cells. In our flotation we endeavor to obtain some degree of froth flotation using pine oil as a frother. The boiling action as caused by increasing the amount of air added to the cells is detrimental to recovery in froth flotation. It is our belief that to obtain increased recovery from a cell in froth flotation, additional air must be introduced but at the same time this air must be dispersed throughout the pulp in the form of small bubbles and this can only be done by increasing the speed of the impeller. Therefore, if Mr. Schiffman decreased the speed of the No. 30 impellers and at the same time continued to use supercharged air, the boiling action may have been increased because larger bubbles developed. The lower recovery as reported could be due to this factor. Decreasing the impeller speed will definitely decrease the power consumed but may have other disadvantages. First, we believe it will permit "sanding" in the cell and this in our opinion will increase the wear on the impeller and diffuser, especially so, if there is pyrite and/or sand present in the feed. "Sanding" in the cell when air is used, as in froth flotation, will effect the dispersion of this air and cause boiling.

Jan 1, 1951

By Sam N. Dewitt, Albert S. Trube

This paper presents a discussion of the pressure maintenance operations which were begun in the New Hope Field. Franklin County. Texas. in 1944. The project has required the injection of extraneous waters at depths from 7.300 to 8.000 ft with intake well-head pressures up to 4.000 psi in three different reservoirs — the Bacon. Hill. and Pittsburg. Records of oil and water production. water injection and the GOR have been kept for each reservoir and reservoir pressures were taken at regular intervals. These data indicate that the Bacon Reservoir had no apparent water encroachment up to the time of water injection. However. the Pittsburg and Hill reservoirs had some natural water influx hut not sufficient to prevent pressures from declining below the bubble point. The Bacon and Hill reservoirs responded almost immediately to water injection. while the Pittsburg which is the least permeable. has shown good pressure response only since .August, 1948. The principle objective of the project has been to increase ultimate recovery. Success of the project to date also has resulted in reduced lifting costs. Esti- mates based on the initial water breakthrough patterns indicate that the primary objective of substantial additional recovery will he accomplished, and there is a possibility that the original estimates elf oil recovery with pres-sure maintenance will he exceeded. INTRODUCTION This pressure maintenance project was one of the earliest primary pressure maintenance programs to he attempted on a multiple zone field. There are three producing reservoirs into which water is being injected for the purpose of maintaining pressure and increasing the ultimate recovery- from each. This paper is limited in scope to al1 account of the development of the project. the pressure production relationship prior to the injection of water and the effect of water injection on the producing reservoirs. Also discussed are the nature of the injection system and the indicated results on initial water break-through in the Bacon Reservoir. FIELD CONDITIONS The New Hope Field, which is located about 12 miles northeast of Winusboro, Franklin County, Texas, is an elongated symmetrical anticline containing four known oil reservoirs. The reservoirs are of the Trinity group of the Comanchean or Lower Cretaceous period and are found in Table I. The oil productive portion of each reservoir is not present in all of the producing wells because their areas and positions vary with respect to one another. Fig. 1 shows the relative position of the four reservoirs and illusIrate? how some wells could penetrate all four, while others are restricted to three. two. or perhaps one. depending on structural location. The first three reservoirs contain undersaturated oil. The deepest. the Elledge, has a primary gas cap. Although this reservoir covers a considerable area of the field. it has a very thin section and a low order of permeability. Elledge producing wells have generally been characterized by an early increase in GOR, making it necessary to recomplete them in other reservoirs. (At present. one well is completed in the Elledge. which is still producing.) Because of the difficulties en-countered in producing oil from this reservoir. and the small quantity of oil actually present. future attempts at producing it will probably be on a salvage basis during the later life of the program. For this reason, the remainder of this report will be confined to a discussion of the Bacon, Hill and pius-burg reservoirs.

Jan 1, 1950

By Frederick T. Williams

THE purpose of this paper is to discuss the relative merits of the large 31/8 in. machine and the small 21/4-in. tappett machine in driving development-headings ; and although the . data here presented were obtained from cross-cut headings alone, experience has shown that the results are equally true in drifting, raising and winning. Recently we drove two parallel cross-cuts through the same formation, using a 3k-in. machine at the breast of one cross-cut., and a 2k-in. machine of the same make at the breast of the other. The results of this work afforded an ideal comparison, since in both cases the headings were advanced through rock practically of the same hardness and breaking-properties ; the amount of sludging was equal, and there was no difference in the condition of the steel or the machines, in the air-pressure or in the experience of the operating-crews. Some operators in the Cripple Creek district contend that there is ground which cannot be handled with the small machine, the holes being too small to contain enough powder to pull the ground, etc. The results obtained in working the property of the Portland Gold Mining Co., however, show that the ground worked by them does not fall in this class. During a period of two years there have been driven, with the small machine, 4 miles and 308 ft. of development-headings, through a diversity of ground, including Pike's Peak granite (a coarsely porphyritic type of granite), highly indurated, andesitic or phonolytic breccia, true massive andesite, trachytic phonolyte, tuffas, and along dikes of decomposed basalt and hard phonolyte; in every instance a satisfactory record was made. The headings here described were driven through highly indurated, andesitic breccia, having a hardness of from 5.2 to 7.2

Mar 1, 1906

By Wido Tilmann

13.6-1. Importance. In Germany there are large tertiary brown coal reserves, most of which are located close to the surface. Therefore, brown coal has been recovered for many years by means of opencast methods. By utilizing a high degree of technology, a rational operation has been achieved, and as a result, the mining techniques have become renowned all over the world. After the war, all the dredgers and overburden spreaders, as well as the means of conveyance, had to be redeveloped for adapting this equipment to the changing conditions of the deposits. Numerous auxiliary machines were adopted from the American earth moving industry and altered according to the different requirements. As a result of such technical developments, the output per man and per shift was increased remarkably in spite of the deterioration of the geological conditions. In the whole of Germany, the total reserves of brown coal amount to 100 billion metric tons, of which 60 billion tons are situated in the Federal Republic of Germany. In the latter area, 8.5 billion tons will be recover- able by opencast means, of which 3.5 billion tons are already developed. The annual output reached 102 million tons in 1965. This total figure comes from four different mining districts: Rhineland, Helmstedt (town at the border of the Soviet occupied zone), Hesse, and Bavaria. The production figures (1965) are as follows: [ ]

Jan 1, 1968

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By L. L. Melton, W. T. Malone

Fluid mechanics research conducted with non-Newtonian fluid systems now permits prediction of the behavior of these fluid systems in both laminar and turbulent modes of flow through circular pipes. Present work concerns non-Newtonian fluid systems currently used in the hydraulic fracturing process. During fracturing treatments, an unsteady-state condition may frequently be encountered arising from. the reaction rate of a chemical additive. This condition must be evaluated in order to predict the actual behavior of a particular fluid during field application. Design and operation of the apparatus used to determine fluid-flow behavior permit obtaining data under such non-equilibrium conditions. This paper shows methods used to obtain rheology measurements, develop hydraulic relationships and evaluate chemical reactions producing unsteady-state conditions. Engineering application of this research is illustrated by employing measured rheological values and developed hydraulic retationships to produce frictional pressure loss (psi/100 ft) us flow rate (bbl/min) charts of common tubing and casing sizes for an example fracturing fluid. How these charts and chemical reaction rate information are then combined to predict actual turbulent hydraulic behavior during unsteady-state field conditions is also discussed INTRODUCTION Many fluids used in hydraulic fracturing contain chemical additives which impart non-Newtonian fluid properties that may drastically alter their hydraulic behavior. Equally drastic alteration in wellhead pressure, injection rate and hydraulic horsepower requirement may result from these fluid properties. Prior research conducted to relate non-Newtonian fluid properties with hydraulic behavior has not as yet produced a universal relationship, particularly for the turbulent flow region. which of the many Possible non-Newtonian fluid properties is responsible has not been conclusively established. A systematic description, suggested by Metzner, of the many possible non-Newtonian fluid properties exhibited by real-fluid behavior, and a current discussion of theoretical and applied aspects of non-Newtonian fluid technoloy can be found in Handbook of Fluid Dynamics. f Little or no research has previously been attempted with fluids exhibiting time - dependent properties. Addition of chemicals during a fracturing treatment is often accomplished by continuously mixing and displacing the fluid. This produces a time-dependent effect or unsteady-state condition while the fluid is progressing through surface and wellbore conductors. This condition is due to solution or chemical reaction of the additive. Considerable departure from conventional methods of obtaining and interpreting data was found necessary to consider these conditions. Therefore methods were developed to obtain hydraulic behavior information under these complex, unsteady-state conditions. Relationships presented in this paper to predict hydraulic behavior of non-Newtonian fluids in circular pipes were obtained by constructing and operating a small pipeline apparatus in the manner of a pilot-plant study. These relationships are suggested as scaleup equations and are not proposed as fundamental rheological parameters. While perhaps deficient from a fundamental research viewpoint, a pilot-plant study does permit the determination and convenient evaluation of variables pertinent to a process. A pilot-plant study can result in a valid engineering application procedure even when fundamental relationships are still undefined. An excellent series of articles by Bowen has appeared in the chemical engineering literature.2-8 These give a thorough review of proposed hydraulic relationships and their limitations for non-Newtonian fluid behavior in circular pipes. A graphical method is presented to scale up data for a fluid exhibiting an anomalous hydrau1ic behavior in the turbulent flow region. Considerable assistance has been obtained from these articles to interpret the anomalous behavior noted during this investigation. These articles also provided assurance that a pilot plant is a practical approach to evaluate the hydraulic behavior of non-Newtonian fracturing fluids. _____________

Jan 1, 1965

By C. M. Brinckerhoff

Safety work in mining at the Andes Copper Mining Company, Potrerillos, Chile, is divided into three parts: (1) accident prevention, (2) fire prevention and protection, and (3) silicosis prevention and control. In the company's operations a steady campaign has been waged to reduce accidents and silicosis, and to prevent fires. In the following pages the safety record for the past twelve years will be examined and the methods explained by which the accident rate was reduced. Table 1 contains yearly data pertaining to the scale of the mining operations and the accident record. Block caving is used for all ore production and the tonnage mined has averaged 30,000 short tons per day for the past seven years. Table 2 classifies 44 fatal accidents which have occurred since 1935. The leading causes of accidental death are transportation of ore and use of explosives, followed in order by persons falling, falls of ground, and by asphyxiation. In the case of serious accidents, however, the greatest cause is falls of ground, followed, in turn, by ore transportation, persons falling, explosives, and asphyxiation. Accident Prevention The improvement of the safety record was obtained by a combination of many factors. In surveying the results at Andes for the past twelve years, it is possible to select some features of the present operation which have contributed to the accident record. The most important of these are: (1) good staff planning, (2) good equipment, (3) an alert safety organization, and (4) education and selection of the workmen. GOOD STAFF PLANNING As a result of good staff planning, the mine has good working conditions, namely, good ventilation, moderate temperatures and humidity, and good lighting. These factors not only reduce accidents but also improve efficiency. In haulage work, accidents have been reduced by having traffic move in a forward direction only. The latter makes possible a one-man train crew. Trains are centrally dispatched from loading drifts which are interconnected by signal lights, so that when a train in a lateral drift is given permission to move into a main line drift, a red light signals in all other lateral drifts in that area. Good track is maintained, and safety niches are required at all switch throws. Since safety niches were provided there have been no fatal or serious accidents at such points. All main line haulage drifts are illuminated by electric lights. Haulage drifts are kept clean. Adequate clearance has been provided between cars and between cars and the sides of the haulage drifts. The 4 1/2 ton Cranby type cars are equipped with roller bearings, and the 10 ton loconlotives with trolley shoes instead of wheels. These two features are responsible for improved ore haulage conditions and contribute to greater efficiency and safety.

Jan 1, 1950