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By R. F. Meel, J. K. Stanley

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By M. T. Martinson, I. W. Nicholson, C. J. Chindgren, F. P. Williams, L. C. Bauerle, S. F. Ravitz

The vanadiferous shales of southeastern Idaho and southwestern Wyoming constitute the largest known reserve of vanadium in the United States.' These deposits have never been exploited except for the relatively small amounts of vanadium recovered by the Anaconda Copper Mining Co. in the treatment of phosphate rock from southeastern Idaho. The maior domestic source of vanadium has been the sandstone ores of southeastern Utah and southwestern Colorado. Early in World War 11, it appeared that these ores could not meet the greatly increased demand for vanadium, so the investigation described in this report was undertaken to develop processes for the recovery of vanadium from the Idaho-Wyoming deposits. The utilization of these deposits became unnecessary, however, because of greatly expanded production from the Utah-Colorado sandstone ores and the continued availability of vanadium from other sources, chiefly Peru. The major use of vanadium is as an alloying agent in the manufacture of high-quality steels. Vanadium constructional steels usually contain 0.05 to 0.20 pct vanadium, which refines the grain and increases the strength, elastic limit, and resistance to shock and fatigue. Vanadium tool steels not used in high-speed work contain 0.10 to 0.60 pct whereas high-speed tool steels contain 1.0 to 4.0 pct. Vanadium compounds are used as catalysts (principally for the oxidation of SO2 to sulphuric acid and of naphthalene to phthalic acid) and in the paint, chemical, ceramic, dye, and printing industries. The selection of the particular ore deposit to be exploited would involve consideration of many factors besides the metallurgical results that might be obtained. Chief among these would be the reserves of ore available, the grade of the ore, and the mining costs. As very little was known about any of these factors, it was necessary to investigate methods of treatment of all the ores under consideration, working with samples obtained in the course of the exploration work, even though they were not positively representative of the whole deposit from which they were taken. Because of wartime conditions prevailing when this investigation was started, first consideration was given to processes that could be put into operation most quickly and would involve minimum use of strategic materials, even though these processes might not be the most economical.

Jan 1, 1949

By John F. Elliott, John P. Hager

The standard free energies of formation of the lowest stable sulfides of chromium, molybdenum, and tungsten in equilibrium with the corresponding metal hazle been determined by reacting the sulfide and metal with H2(g)/H2S(g) mixtures. The reaction is A method for estimating the standard ~nolav entropies and standard entropies of formation at 298°K of the sul-fides of refractory metals is presented. The standard free energies of formation of the lowest sulfides of the metals in group VIa of the periodic table are probably best determined with the reaction* is known with greater accuracy than is that property for any other sulfur-bearing compound or solution which might serve as a reference phase to establish the chemical potential of sulfur for the essential re- However, there still remain significant problems to the use of Reaction [I] in studying these sulfides. First, the equilibrium gas ratios (Ph2S/PH2) are very small, and with the most stable sulfides in the series the ratios tend to be at the limit of the range for precise chemical analysis (10-4); and second, the reaction rate for the formation or reduction of these sulfides appears to be relatively slow. A primary reason for the latter problem is that the gas phase near the equilibrium concentration has very little capacity for transport of sulfur. It is to be noted that the thermo-dynamic properties obtained from the experimental results by Eq. [I] apply for 1 g-atom of sulfur in the metal-saturated compound even though the exact composition of the compound has not been determined. The work reported here is a study of the standard free energies of formation of the lowest sulfides of chromium, molybdenum, and tungsten, and of copper, by Reaction [I]. In planning the experimental program, it was decided that the technique that has been used previously3"' could be used with modification and that an improved analytical method was needed for determining H2S in the gas phase. THE EXPERIMENT The once-through flow of gas was selected in preference to recirculating the gas, a) because of the low sulfur capacity of the gas, b) because of the relatively slow rate of reaction and the danger of the

Jan 1, 1968

By Thomas M. Drown

The use of bromine as an oxidizing agent, particularly for sul phur, has become very general in analysis, replacing the stronger oxidizing acids. The object of this paper is to describe briefly the experience which we have gained with this reagent in the laboratory of Lafayette College in the oxidation of metallic sulphides. Most of the simple sulphides, as blende, pyrite, etc., when exposed to the combined action of an alkaline hydrate and bromine, and finally to hydrochloric acid, are completely and promptly dissolved. The procedure is as follows: The very finely pulverized mineral is first treated, in a beaker, with a solution of sodium hydrate of a spe cific gravity of 1.25, and heated ; bromine is then cautiously added to supersaturation, and finally hydrochloric acid to acid reaction. If any of the sulphide is not taken up, the same operation may be re peated. It is necessary, however, that the mineral be very finely pulverized. Instead of using the pure bromine, a saturated solu tion of bromine in potassium bromide may be used with equally good effect. The process is advantageously simplified by making a saturated solution of bromine in the concentrated alkali. This is done by pouring bromine into a solution of sodium hydrate, of the above given specific gravity, until no more is taken up, and then adding a little of the sodium hydrate solution until the liquid does not give off free bromine. The procedure with this solution is as follows: The pulverized mineral is moistened with, say, 10 cc. of the solution, and heated, then hydrochloric acid added to just acid reaction. Two more additions of the alkaline solution, in amounts of 20 cc. each, are added at intervals of about ten minutes, each addition being followed by hydrochloric acid. The total amount of the alkaline solution (containing the bromine) used is, therefore, 50 cc., and the amount of hydrochloric acid should not exceed that necessary to make the solu tion acid after each addition of the alkali. The mixture should be kept hot. After the final addition of acid, the contents of the beaker is taken to dryness and heated in an air-bath to 110° to 115°C., to render silica insoluble. The dry mass is then taken up by hydro' chloric acid and water and, after filtration, the sulphuric acid is pre

Jan 1, 1880

R. B. BRinsmade, Ixmiquilpan, Hgo., Mexico (written discussion").—how far ahead of the United States are the self-governing British colonies in their application of economic democracy is well illustrated by Mr. Godson's paper. To prove this, I need quote only two of his assertions, the italics being mine: "lt is a stern fundamental principle that a11 natural resources are the inalienable property of the crown.'' "The right to a claim should only exist as long as it is worked or taxed to insure work. Once depart from that sound maxim, there results improper control of the natural resources of the country, which primarily belong to the people." These assertions formed the basis of my criticism1 of Dr. Raymond's paper in 1913, and they should be inscribed in letters of gold above the entrance to the office of every county recorder in the United States. I venture to assert that the existing United States mineral land laws are essentially unfair to the nation and a hindrance to the legitimate miner, because they fail to embody the above quoted principlca; and this applies both to state laws east of the Mississippi and to federal laws in the West. That these laws favor the forestaller and the monopolist, defraud the government of its fair share of the profits of mineral production, and tend to industrial feudalism must be evident to any competent unbiassed observer. The fact that no serious political movement arose to change them, until the conservation agitation of the last decade, may be largely explained by two salient conditions. First, as stated by President Winchell, "for a long time there was such a vast surplus, or excessive amount of unwanted, undesirable land in the West that the land offices did not scrutinize the claim sought to be located;" second, that the millions of individual farm owners throughout the country could easily be aroused, by the special pleaders hired by the great land speculators and monopolists, to use their vast political power for the suppression of any statesmen striving to incorporate in our semi-feudal land laws any such principles as those quoted from Mr. Godson. While agreeing with Mr. Godson that a freehold or fee-simple title, if coupled with obligatory continuous work, may have the same practical effect as a lease, it seems to be the experience of the most active and

Jan 1, 1920

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940

By W. H. Young, P. D. Torrey

The Eastern fields comprise a distinct geological and geographical unit, located in the northern part of the Appalachian geosynclinal prov-ince. In this area are the fields of New York, producing from rocks of Devonian, Silurian and Ordovician age; the fields of western Pennsylvania, where oil and gas occur chiefly in rocks of Mississippian and Devonian age; the fields of eastern Ohio, where oil and gas are obtained from rocks of Pennsylvanian, Mississippian and Silurian age; and the fields of West Virginia, where oil and gas are produced from rocks of Pennsylvanian, Mississippian and Devonian age. Many of these fields are of great antiquity in comparison to the age of the producing areas in a greater part of this country, and consequently in most instances it is impossible to obtain accurate historical statistics. In addition, the records of many of the more recently discovered fields are either unobtainable or are not sufficiently reliable to justify their incorporation in a review of this character. Rather than overemphasize certain fields and areas, where complete records are available, when there are many other fields of equal importance for which statistical data are not available, the authors have made a tabulation of development that does not take into consideration past operations and production. The records utilized in preparing this paper were derived largely from the scout reports of several of the larger companies, which generously made them available to the authors. These were independently tabulated by counties and townships, in order to eliminate as far as possible duplications and, excepting the Clinton fields of Ohio, where many of the smaller wells have not been individually reported, they represent the most accurate information available. Market conditions in both the oil and gas industry were far from favorable during 1932 and in consequence there was a total decline in drilling in the Eastern States, which is 22 per cent less than the number of completions in the preceding year. This decline was not constant over the entire area, as is shown in Table 1. The oil fields of both New York and western Pennsylvania were the scene of renewed drilling activity, which was largely restricted to the water-flooding operations in the Bradford and Allegany fields. Practically no new operations were started, but a certain number of new wells

Jan 1, 1933

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

The National Research Council was organized in 1916 at the request of the President by the National Academy of Sciences, under its congressional charter, as a measure of national preparedness. The work accomplished by the council in organizing research and in securing cooperation of military and civilian agencies in the solution of military problems demonstrates its capacity for larger service. The National Academy of Sciences is therefore requested to perpetuate the National Research Council, the duties of which shall he as follows: 1. In general, to stimulate research in the mathematical, physical, and biological sciences, and in the application of these sciences to engineering, agriculture, medicine, and other useful arts, with the object of increasing knowledge, of strengthening the national defense, and of contributing in other ways to the public welfare. 2. To survey the larger possibilities of science, to formulate comprehensive projects of research, and to develop effective means of utilizing the scientific and technical resources of the country for dealing with these projects. 3. To promote cooperation in research, at horse and abroad, in order to secure concentration of effort, minimize duplication, and stimulate progress; but in all cooperative undertakings to give encouragement to individual initiative as fundamentally important to the advancement of science. 4. To serve as a means of bringing American and foreign investigators into active cooperation with the scientific and technical services of the War and Navy Departments and with those of the civil branches of the Government. 5. To direct the attention of scientific and technical investigators to the present importance of military and industrial problems in connection with the war, and to aid in the solution of these problems by organizing specific researches. 6. To gather and collate scientific and technical information, at home and abroad, in cooperation with governmental and other agencies, and to render such information available to duly accredited persons. Effective prosecution of the council's work requires the cordial collaboration of the scientific and technical branches of the Government, both military and civil. To this end representatives of the Government, upon the nomination of the National Academy of Sciences, will he designated by the President as members of the council, as heretofore, and the heads of the departments immediately concerned will continue to cooperate in every way that may be required. THE WHITE HOUSE, WOODROW WILSON. 11 May, 1918.

Jan 7, 1918

By John Birkinbine

(Read at the Philadelphia Meeting, February, 1878.) IN a former paper* attention was directed to the various firms of pumping machines employed for permanent work in mining and metallurgical processes. The following is simply a collection of memoranda of work done of a temporary character, and is presented by way of comparison with other work of similar nature. In close proximity to the charcoal furnace at Pine Grove, Cumberland County, Pa., is a large deposit of superior hematite iron ore, which has been worked for a number of years, and from which many thousand tons of ore have been taken by open pit workings. In July, 1874, the furnace was blown out and operations at the bank suspended, the machinery for draining being removed except a plunger pump, 18 inches in diameter and 66 inches stroke, operated by a steam-engine by means of rods. The pit was allowed to fill with water, and no steps towards its reclamation were taken until November, 1877. At that time the pit was a pond of water at the base of the mountain, having an area of about four acres and a depth of seventy feet. As the pumps, rods, etc., had been submerged for over three years, and partially buried by the mud washed down from the banks, and as it was determined to change the location of the pump for future operations and drive it by water-power, a temporary pumping apparatus was determined upon for reclaiming the pit and keeping it drained until the permanent arrangements could be completed. By opening an old adit about 10 feet of the water was removed, and the area decreased to three acres. The inflow of springs was found to be 250 gallons per minute, and the amount of water contained in the pit was computed to be 45,000,000 gallons. As the inflow would undoubtedly increase while the water sank in the pit, provision was made for removing at least 60,000,000 gallons, at the rate of 1,500,000 to 2,000,000 gallons per day. The company determined to employ a Heald and Cisco centrifugal pump driven by an oscillating engine by means of a belt. Steam was supplied by four plain cylinder boilers, each 36 inches diameter *Transactioiis of the American Institute of Mining Engineers, vol. p. 455.

Jan 1, 1878

By D. E. Buchanan

The: volatility of a motor fuel is an index to its quality and to the satisfaction that will attend its use as an internal combustion engine fuel. Natural gasoline is concentrated volatility; threfore, it is quite natural that the most important market for natural gasoline should be for blending with less volatile refinery gasolines. Progress in the art of manufacturing natural gasoline, particularly in fractionation, which has made possible the elimination of the fixed gases and lighter hydrocarbons having a tendency to gasify at atmospheric pressure and temperature, has made it possible and desirable for refiners to utilize an ever-increasing percentage of natural gasoline in their finished product. This, in turn, has enabled the industry at large with each succeeding year to supply to the consuming public a better grade of gasoline. While cracking processes and improved fractionation in refinery operation have resulted in higher yields of gasoline per barrel of crude oil refined, natural gasoline has also played a large part in this respect because it has enabled the refiner to cut deeper into the crude and still maintain proper standards of volatility by blending natural gasoline with the product from his stills. There is, of course, with even the present improved grades of natural gasoline, a limit to the percentage that may properly be used. This percentage varies with different grades of crude oil, varies according to the facilities employed at the refinery and varies according to the grade of motor fuel manufactured; therefore it is not possible to say that for a certain predetermined amount of motor fuel to be manufactured in a given area, a certain definite amount of natural gasoline will be required. It is, however, generally conceded, and statistics bear out the statement, that the average gallon of motor fuel sold in this country contains approxi-matcly 11 per cent. of natural gasoline. Isolated cases may be found where in a very few refineries during certain seasons no natural gasoline is used, while in other plants as high as 35 per cent. and 40 per cent, natural gasoline is used in certain grades of motor fuels. Production Statistics The total production of natural gasoline for 1927, including California, is estimated at 1,627,600,000 gal. This represents an increase of 20 per

Jan 1, 1928

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By C. L. Prokop

A laboratory investigation has been made of the effects of mud hydraulics upon the formation and erosion of mud filter cakes. The tests were conducted to simulate drilling conditions as nearly as possible. The formation of mud filter cake in a drilling well does not proceed at a uniform and unbroken rate. Instead, the rate of cake accumulation depends upon whether or not the mud is being circulated. If the mud column is quiescent, filter cake formation is a smooth function of the filtration characteristics of the system. If the mud is being circulated filter cake formation depends not only upon the filtration characteristics of the mud but also upon the erosive action of the flowing mud column Filter cakes formed during continuous mud circulation were observed to reach an equilibrium thickness after several hours' circulation. Mud circulation was maintained at a constant volumetric rate throughout each experiment. The fluid velocity at equilibrium cake thickness was dependent upon the thickness of the filter cake. Muds having exceptionally high water loss deposited thick filter cakes in spite of very high eroding velocities. The muds having good filtration characteristics deposited thin filter cakes at equilibrium circulating velocities well within tile range of those in a drilling well. It was observed that filter cakes deposited during stagnant filtration were quite difficult to erode by mud circulation. The - rate of crosion computed from the rate of filtrate accumulation after equilibrium cake thickness had been reached was in reasonable agreement with the rate of erosion obtained by direct observation. Continuous mud circulation usually caused the permeability of the filter cake to decrease with time. INTRODUCTION Many of the difficulties encountered during tile drilling of a well have been attributed to the loss of water from the mud and the attendant deposition of solids upon the walls of the hole. Past experience has shown that a reduction of the filtration rate of the drilling fluid eliminates or greatly reduces these difficulties. Definite filtration requirements, however, are hard to establish for a given set of conditions. This is due. in part, to the fact that the usual filtration test performed upon mud doe? not simulate well conditions as closely as desirable. The filtration characteristics of a mud are customarily determined by means of the standard low-pressure API wall-building tester.' In this instrument a filter cake is deposited upon a horizontal bed under a pressure differential of 100 psi. The rnud is quiescent during the filtration period. In actual practice. mud filtration occurs within a well under quite different conditions. One of the major differences is that mud flows upward across the filter bed as the filter cake forms. This undoubtedly produces a change in the filter cake which cannot be reflected in the results of the API test. The laboratory work described in this paper had as its primary objective a better understanding of the influence of mud circulation upon the thickness and ,characteristics of the filter cakes deposited under conditions similar to those existing in a drilling well. ANALYSIS OF PROBLEM Once a permeable formation is penetrated by the bit, filtrate from the mud flows into the formation. 'he mud solids plaster against the walls of the hole, forming a filter cake. If the mud column is stagnant, that is, if it is not being circulated. the filter cake will increase in thickness until the hole is filled. Prior to the time that the hole is filled, the thickness of filter cake existing at any given time will be a function of the filtration characteristics of the mud, the temperature, and the pressure differential. The effects of these variables have been investigated in the past for both flat bed filtration2'3 and for radial filtration.' When the mud is circulated in a hole in which a filter cake i. being deposited. some of the solids that would ordinarily deposit in the filter cake will be carried away by the eroding action of the mud. This will limit. filter cake thickness. Some work has been done to determine the effect of flow upon the filtration rate in a circulating mud system' but little work has been done upon the factors which determine the filter cake thickness existing in a circulating system. On first sight it would appear that the major factors controlling filter cake formation in a circulating system should be: 1. The rate of deposition of solids from the mud. 2. The erosive force that the flowing mud exerts upon the filter cake. 'A. The erodabilitv of the filter cake. 4. Any change in filter cake characteristics attributable to the scouring action of the mud. The rate at which solids are deposited from the mud will be controlled to a large degree by the filtration characteristics of the mud, the pressure differential. the temperature under

Jan 1, 1952

By N. Mungan

Laboratory imbibition and displacement experiments were performed using crude oil and cores drilled with water and preserved under anaerobic conditions. The purpose of these tests was to determine reservoir rock wettability and to find out if more oil could be recovered by use of NaOH solution than by conventional waterflooding. The preserved cores were found to be oil-wet. Contrary to work in the literature, these cores changed to water-wet upon contact with air. After exposure to air for a week, the cores yielded more oil by waterflooding than when preserved under exclusion of air. At reservoir temperature of 160F, flooding the preserved cores with 0.5N NaOH solution recovered more oil than an ordinary wa-terflood, and additional oil when following a waterflood. When the caustic solution was used from the beginning, all the extra oil was obtained before breakthrough; when the caustic followed a conventional waterflood, the extra oil was produced in the form of an oil bank ahead of the injected caustic. The increase in oil recovery resulted from wettability reversal. Also, use of caustic reduced the volume of injection required to flood out the cores. At room temperature, however, the caustic solution did not reverse the wettability and gave no additional oil recovery. Cores which had become water-wet by air exposure or caustic flooding were restored to their original oil-wet state when saturated with crude oil and allowed to equcilibrate at reservoir temperature for two weeks. Therefore, in the absence of preserved cores, it may be possible to restore weathered cores to their original wettability for use in laboratory floods. INTRODUCTION Waterflooding has been in use since 1865, and is by far the simplest of secondary recovery methods. Unfortunately, most waterfloods are inefficient in recovering oil, often leaving half or more of the original oil in place un-recovered. The low oil recovery generally results from low sweep efficiency and low displacement efficiency. Consequently, to increase oil recovery by waterflooding, sweep and displacement efficiencies should be improved. Sweep efficiency is primarily affected by reservoir heterogeneities and mobility ratio, while displacement efficiency is affected by the capillary forces between fluids and rock surfaces. For petroleum reservoirs, the capillary forces are expressed in terms of interfacial tension and wettability. If oil recovery is to be improved significantly in water- flooding, the capillary forces holding the oil in the raervoir porous matrix must be reduced or eliminated. One way to reduce capillary forces is to inject commercial surfactants ahead of the injection water into the reservoir. Laboratory tests of this method have shown no promise of an economical process yet, and no increase in oil recovery was obtained in the field trials which have been reported. Work is continuing in many companies to find surface-active agents which, in workable concentrations, can yield substantial added oil recovery. Another way to change capillary forces operating in petroleum reservoirs is by changing the pH of the injected water. Wagner et al.' showed that change in the pH sometimes activates the surface-active materials natural to some crudes and brings about gross wettability change. Since pH alteration can be obtained with cheap chemicals, such as hydrochloric acid or sodium hydroxide, the process shows promise of being economical in a field application. Pan American Oil Corp. reported oil recovery by use of caustic solution from a flooded-out reservoir.' Their test, conducted at a small additional cost, yielded results which were so sufficiently favorable and encouraging that the wettability reversal flood was expanded to portions of the field not previously flooded.13 It is important to bear in mind that changes in the pH of the water not only can reverse wettability but also can lower the interfacial tension between water and crude oil. Reisberg and Doscher4 have studied the pH dependency of the interfacial tension of Venture crude using sodium hydroxide solutions of various concentrations. Their data show that the interfacial tension was lowered from 23.0 to 0.02 dynes/cm by increasing the NaOH concentration from 0.005 to 0.5 per cent by weight. Thus, the use of NaOH may lead to additional oil recovery due to both wettability reversal and lowering of interfacial tension. Whether alteration of pH results in wettability reversal from oil-wet to water-wet and increases oil recovery depends on wetting properties of the reservoir rock and the crude. This necessitates delicate laboratory experiments, with suitable core and fluid samples from a field. Although many investigators have studied wettability reversal floods in the laboratory,1,2,5,6 these studies have been carried out with synthetic porous media, refined laboratory fluids and surface-active chemicals to simulate the process. The study presented in this paper is the first time that wettability reversal by pH alteration has been accomolished in laboratory core floods using carefully preserved natural cores, live crude and with experiments performed at reservoir pressure and temperature.

Jan 1, 1967

By Wm. R. Dotson

Forty years ago the atom was split and the Age of Fission dawned. Uranium was the element used in this earth-shaking accomplishment. Thitherto almost unknown to the man in the street, uranium soon became widely and persistently sought. And the quest for this unique material is not likely to diminish during this century. To find is one thing; to own is another. Who owns uranium in the ground? Where no mineral rights in the land have been severed by devise, grant, reservation or lease, the uranium belongs to the fee simple owner of the land. But where there has been a conveyance or reservation of all or part of the "minerals", determining WHAT a substance is has been the traditional way of determining WHO owns it. What, then, is this element called uranium? The 1907 edition of Watts Dictionary of Chemistry calls it "a lustrous, hard, silver-white metal". Of nature's three prime divisions it falls within the embrace of the mineral kingdom - substances neither animal nor vegetable. In its natural state uranium always is combined with other elements or substances in the form of an ore mineral. May we, then, put to rest any doubt or question as to the nature of uranium and classify it for all purposes, including that of ownership, as mineral? Not quite! That self-same logic would find oil and gas primly ensconced in the animal or vegetable kingdom. Technically, oil and gas are not minerals but legally they have been classified as such. Why? The Supreme Court of Tennessee sought the answer in 1897 in the case of Murray v. Allard, 43 S.W. 355. After citing authorities pro and con, and while admitting their origin to be "decomposition of marine or vegetable organises" that court firmly concluded that since they were obtained by a form of mining, oil and gas were minerals. From the above example two elementary truths emerge. First, for purposes of ownership, uranium is and will be whatever the courts say it is. Secondly, the courts historically and currently favor a practical rather than technical test to determine the "mineral" character of a substance. So now we turn to the jurisprudence for enlightenment and definition. EARLY CASES ALLOT URANIUM TO MINERAL OWNERS Two early cases involving the ownership of uranium followed what had been well-settled mineral within the meaning of the conveyances involved, confirming ownership in the mineral owners. In 1956 the U. S. District Court for New Mexico in the case of New Mexico and Arizona Land Company v. Elkins, 137 F. Supp. 767, appeal dism'd 239 F.2d 645 (10th Cir. 1956), found that a 1946 deed reservation of "all oil, gas and minerals underlying or appurtenant to said lands" included uranium and thorium. The court reasoned that uranium and thorium, being minerals within the scientific, geological and practical meaning of the term, would certainly constitute minerals within the purview of the reservation. While agreeing that uranium and thorium were "minerals", defendants argued that at the tine of execution of the conveyance it could not have been the intention of the parties to reserve them because they had no commercial value in the locality and were, in fact, not known to there exist until their later discovery in 1950. The court re¬jected, as a matter of law, this "lack of knowledge" theory citing the Supreme Court of Kentucky holding in Maynard v. McHenry, 113 S.W. 2d 13, that: "The mere fact that a particular mineral has not been discovered in the vicinity of the land conveyed or is unknown at the time the deed is executed rules of construction and held that uranium was a does not alter the rule . . ." that a grant or exception of "mineral" in a deed includes all mineral substances which can be taken from the land unless restrictive language is used indicating that the parties contemplated something less general than all substances legally cognizable as minerals. Further, argued the defendants, the only feasible mining procedure for such substances was open pit or strip mining, which would destroy the value of the land for grazing or agriculture. Finding that the language of the reservation was clear and unambiguous, the court would not permit the admission of extrinsic evidence as to mining procedures required. Elkins is the first uranium case construing the granting clause involved. In 1958 the Texas Court of Civil Appeals at San Antonio, in Cain v. Neuman, 316 S.W. 2d 915, no writ, held that a 1918 lease conveying "all of the oil, gas, coal and other minerals in and under" the land involved covered uranium. The lease provided a royalty of 1/10th on "other minerals." "We find no Texas precedent which discusses uranium," said the court, "but the usual arguments that uranium is not embraced within a lease are that the ejusden generis rule excludes uranium from the meaning of the lease

Jan 1, 1979

By William Y. Holland, Roger H. Cook

Dexter H. Reynolds (Chapman and Wood, Mining Engineers and Consulting Geologists, Albuquerque, N. M.)—A number of questions are raised by conclusions and inferences made in the above-mentioned paper. The more troublesome of these concern use of the various pozzolans to combat the deleterious effects of the alkali-aggregate reaction. The most alkali-reactive materials listed are opal and rocks containing opaline silica. The pozzolans mentioned specifically for use as amelioratives are opaline shales and cherts. These are stated to retard the expansion caused by the alkali-aggregate reaction. Another well-recognized pozzolan is diatomaceous earth, which consists principally of opaline silica. A pozzolan presumably owes its effectiveness to its high reactivity with the alkaline liquid phase of the concrete mix. It appears reasonable to expect that finely divided opaline silica added as a pozzolan would be more susceptible to reaction with the alkalies present than would larger particles of the same material. The authors report that work with high and low alkali cements indicates that in the presence of alkali-reactive materials, deleterious expansion depends upon the alkali content of the cement. The total effect, therefore, should be more or less independent of the amount of reactive aggregate present, and still more independent of its state of subdivision. The deleterious effects should, if anything, be aggravated by the addition of a finely divided, highly reactive pozzolan. Further, if the alkali-aggregate reaction is of great importance in the long-term soundness of concrete structures, the addition of a pozzolan to a concrete made with aggregate free from known deleterious materials would be a questionable procedure. The benefits reportedly accruing from such use of pozzolans are greater ultimate strength for a given cement content, increased resistance to deterioration by exposure to sulphate solutions and other mineral waters, and greater resistance to damage by wetting and drying and freezing and thawing. In view of the deleterious effects of highly reactive materials are these benefits ephemeral? The same considerations apply to another alkali-reactive material, chalcedony, which appears to consist of ultrafine-grained quartz, with opal absent in detectable amounts. Quartz flour is notably reactive chemically and physiologically (cf. Ref. 11 of Holland and Cook's paper), a fact borne out by its effectiveness as a pozzolan, which presumably might be expected to offset the deleterious effects of the presence of chalcedony in the aggregate. A second question of some importance concerns the reportedly highly deleterious reactivity of acidic and intermediate volcanic glasses, such as rhyolite, perlite, and pumice. Air entrainment is listed as one of the ameliorative measures to combat the deleterious effects of the alkali-aggregate reaction. The alkalic-silica gel formed by the reaction may expand into air bubbles and thus not cause appreciable expansion of the concrete mass. It would appear then that pumice and perlite, particularly perlites of the pumiceous types and other types after expansion, would also tend to counteract the expansion, since these materials consist largely of voids and air bubbles. Certainly this would be expected of structural concrete in which pumice or perlite is used as total aggregate. Finely ground pumice, perlite, and volcanic ash have been demonstrated to be active pozzolans (cf. Pumice as Aggregate for Lightweight Structural Concrete by Wagner, Gay, and Reynolds, Univ. of New Mexico Publications in Engineering No. 5, Albuquerque, 1950). In fact, the term pozzolan was first associated with finely divided pumice or volcanic ash. Such materials were used with hydrated lime as the sole cementitious agent in constructing public buildings, roads, and aqueducts by the ancient Romans. The deleterious alkali reactivity of the volcanic glass, itself containing several percent of the alkalies, apparently did not contribute to the remarkable state of preservation of those ancient structures, as exemplified by the Appian Way and the Pantheon Dome. Still a third question involves .the reactivity of constituents of concrete when exposed to various salt solutions. Resistance to. deleterious expansion and cracking as a result of contact with mineral waters and its relationship to the mineral content of the aggregate are not mentioned by the authors. Yet the phenomena pictured in Fig. 1, and especially in Fig. 2, appear very much like those caused by exposure to mineral waters. The deterioration of concretes exposed to sulphate waters is generally considered related to the chemical constituency of the cement itself, particularly to the relative amount of tricalcium alum-inate contained. Could not many of the ill effects presently blamed on alkali-aggregate reaction really have been caused by contact with sulphate or other salt-containing mineral waters? Or perhaps their use as mixing waters? May not the deleterious expansion be as much a function of the chemical makeup of the cement as it is of the mineral constituency of the aggregate? Would it not be just as important to use alkali-free mixing water as it is to use a low-alkali cement? It appears obvious that resistance of cements and concretes to sulphate and other salt solutions cannot be left out of account in discussion of deterioration of concrete structures with time. This factor may be of equal or even greater importance than the alkali-aggregate reaction, particularly for concrete subjected to wetting and drying cycles, such as airstrip paving, water-retaining dams, and highway structures. Another very important factor is called to attention on page 1022 of the article in Mining Engineering, October 1953, in that failure of concrete structures may result from poor construction practices and use of too high water-cement ratios. Both of these can contribute remarkably to decreased resistance to attack by sulphate waters, and presumably could have an equally remarkable effect upon extent of damage resulting from the alkali-aggregate reaction. From the above remarks it appears that while alkali-aggregate reaction may be an important factor in decreasing the useful. life of a concrete structure, it is not the only factor involved, and it may not be even a controlling factor. Likewise, many of the phenomena apparently associated with the alkali-aggregate reaction may have resulted from cond'itions which had little relationship to the alkali-reactivity of a constituent of the aggregate. Certainly if alkali-aggregate reactivity is a major factor in bringing about early failure, one cannot help feeling anxiety concerning the future of the many concrete structures in this country and abroad in which pumice and perlite were used as total or partial aggregates. This anxiety can only be dispelled by calling to mind that among the best-preserved relics coming down to us from ancient times are structures made with mortars containing highly alkali-reactive aggregates.

Jan 1, 1955

By R. E. Barnes

An overall view of the perlite industry is concisely presented. The geology, mining, milling, processing, and applications of perlite, as well as the present status of the perlite industry are treated. Perlite, in strict petrological usage, describes a specific variety of volcanic glass in which strain, incident to cooling, yielded a concentric structure of fracturing which may be visible either to the naked eye or under a microscope. In commercial usage, the term perlite includes any naturally occurring acidic glass of volcanic origin that will expand when heated to a suitable temperature. The name perlite is a derivation of perlstein which originally defined "certain glassy rocks (hyaloliparites, hyalo-rhyolites) with numerous concentric cracks, from the fancied resemblance of broken out fragments to pearls."1 While perlite has been known to geologists for many years, it was not until 1941, while investigating perlite for use in enamel, that an assayer in Superior, Ariz., noted the unusual expansion characteristics of the ore. Further investigations were delayed until following World War II when many small plants were built and experimentation in the treatment and uses of perlite began. The Perlite Inst. was organized in 1949 to promote the development of the new industry, establish commercial standards through research, and to explore new uses and markets. The Institute, located in New York, represents some 50 producers in the U.S., Canada, Australia, England, France, Germany, Greece, Japan, Mexico, and New Zealand. In 1949, 71,l002 short tons of crude perlite were produced, sold or used by U. S. producers, and this figure increased to 325,0003 short tons by 1959. Such a rate of increase indicates the rapid and continuing growth of the perlite industry. GEOLOGY Perlite ore in its crude form has been found in seven of the mountainous western states, since un-devitrified siliceous volcanic rocks are limited to this section of the U. S. Commercially operated perlite deposits are normally of Eocene and Oli-gocene age.4 These deposits are often several hundred feet thick and may extend over hundreds of acres. In 1959, 13 companies in six states produced crude perlite, although the output in New Mexico comprised 79 pct of the total domestic crude output. Other states in order of their production were: Nevada, Arizona, California, Colorado, and Utah.5 Foreign deposits of perlite which are either producing or under exploration are Australia, Canada, Greece, Hungary,6 Iceland, Ireland, Japan, Mexico, New Zealand, and Sardinia. The ore may exhibit a variety of characteristics depending partially on its water content and eruption history and may range through many shades from black to white. While these characteristics may vary slightly among deposits, perlite ore from a particular source is normally quite uniform. Available chemical analyses of perlites from a large sampling of domestic deposits were recently assembled by the Technical Committee of Perlite Institute and are presented in Table I. While the ranges given do not apply to a particular perlite, they are an indication of the chemical analysis which may be expected from any presently commercially operated deposit. The specific gravity of the perlite ore ranges between 2.2 and 2.4, and its bulk density when crushed and sized is 75 to 90 Ib per cu ft. MINING AND MILLING Perlite ore is quarried from open pits by conventional power equipment, although blasting has been occasionally employed. The rock is then stock-piled until needed. While the milling of perlite may seem a simple process compared to that required for basic metals, or even other nonmetals, the need for accurate control of particle size becomes extremely important in further processing. The first step in this operation is the primary crusher, which is normally a jaw crusher. Following crushing, the material is dried, if necessary, in a rotary dryer and conveyed to a secondary grinder which may be a rod mill, hammer-mill, or cone crusher. However, the crushing characteristics of the perlite, caused by incipient cooling fractures, requires it be removed from the grinding operation once it is reduced to the required size so as to prevent overgrinding. Following the grinding operations, various size screens are used to separate the ore according to particle sizes required for particular uses. Most plants use two or more stages of crushing with perhaps four stages of screening.

Jan 1, 1961

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969