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By F. Twyman

PART I.-QUALITATIVE, SPECTRUM ANALYSIS THOSE chemists (they are still greatly in the minority) who use the spectroscope, use it very often, and find it almost indispensable. As a means of detecting minute quantities of the metals it is unrivalled. A metal can be readily distinguished in the presence of any other element, compound, or mixture without the necessity of separation. The qualitative analysis of the metallic constituents of a substance, which, the spectroscope gives so easily, is a sure basis for planning a chemical analysis. As the determination of each element proceeds the purity of precipitates maybe checked as often as desired. If, possessing these advantages; the spectroscope has been neglected in general chemistry, it is not surprising that it was neglected in metallurgical chemistry; for many of the impurities which are of industrial interest, even when they are present in a metal or alloy in small quantities, are not then always easily detected by the examination of their visible spectrum. The history of the development of the art has been given in Bureau of Standards Scientific Paper No. 444.

Jan 1, 1928

By William P. Blake

IntroductioN.............989 The Blake stone- Breaker Prize.......989 Great Labor-Saving Inventions.. 990 I. Biographical NoticE OF the Inventor......990 II. Former Methods of Breaking Stone......992 Ragging and Spalling......... 992 Cornish Rolls..........993 III. Construction of the Blake Stone-Breaker.. .. 993 The Lever.Pattern.........994 The Eccentric Pattern.........997 The Challenge Pattern......... 999 The Monarch Pattern.........1001 The Multiple-Jaw Pattern........1001 Movable Dies for Jaws......... 1004 Cheek.Plates,..........1007 IV. The Capacity OF Blake Breakers......1007 Position and Feeding of Breakers...... 1008 V. Gyratory Jaw Crushers.........1010 The Gates Rock- and Ore-Crusher......1010 The Comet Crusher.........1010 VI. Some Unusual Forms OF the Breaker......1010 The Smith Hydraulic Pattern.......1012 The Forster Crusher.........1012 The Stafford Crusher.........1013 The Gates Crusher.........1013 The Dodge Pattern.........1013 The Rawson Crusher.........1014 The Duplex Breaker.........1015 Booth's Modification of Wedge-Block......1015 Marsden's Eccentric Pattern.......1017 The Lancaster Machine........ 1017 VII. Combined Crushing and Grinding Impracticable,. . 1018 The Hanscomb Machine ...1019 Howland's Crusher and Pulverizer..1020 The Oliver Crusher and Pulverizer..1021

Jan 1, 1903

By COURTNEY DE KALB

IRON ore is the cause of the present trouble in Morocco. At least three nations are interested in the outcome and private syndicates have been active. The iron deposits are found in that mountainous northern coast line known as the Rif. This is an uplift that has been cut through, by the northward drainage, representing an ancient land surface. Erosion has produced .a fiordlike coast, which circum- stance has aided contraband' traffic to the tribes dominated by Abd-el-Krim, the chief of the clan of the Beni Urriaguel, near the center of 'the north coast, opposite Alhucemas. The iron deposits are extensive in the territory of the Beni Urriaguel. They were "located," if such a term is permissible, many years ago. The first arrangements, through direct contracts with the tribal chieftains, have been reinforced by compliance with the subsequent code under the Spanish protectorate in 1914. Under those terms, the location had to be made through the Arbitral Commission sitting in Paris. These locations, or "denouncements," were made by the I-louse of Mannesmann, of Hamburg.

Jan 1, 1925

By Walter Miller

Crude oil stocks were some 10,000,000 bbl higher on June I, 1947, than at any time during 1946 but the extremely heavy refinery runs the last half of 1947 cut crude inventories to approximately the 1946 closing level of 225,000,000 bbl. Many refiners were seriously short of crude oil during the year. This shortage was reflected in numerous advances in the posted price of crude, justified in part as an incentive for more production but more generally due to competitive bidding. Some purchasers of crude, endeavoring to keep their plants running, resorted to the payment, either directly or indirectly, of premiums above the posted price. Another common practice employed by some suppliers of crude oil was to demand refined products in exchange or trade for their raw material. The refined products picture has darkened in spite of record throughputs. Stocks of gasoline and light and heavy fuel oils were uncomfortably low at the beginning of the year and were in general still lower at the close. The rationing of some products, principally gasoline, to dealers and stations? initiated during the year, gained momentum as stocks continued to diminish. The emphasis placed by the manufacturers of oil-burning equipment on the convenience and economy of heating with oil, together with the tight situation in coal, has developed a tremendous demand for burning oils. Consumption of liquefied petroleum gas for domestic and household fuel had more than doubled in 1946 over 1943, and the demand seems to be limited only by the ability of the equipment builders to furnish necessary storage. transportation, and burning equipment. The supply situation is likely to become more acute in 1948. Demand for petroleum products is being pushed to new heights not only by the unprecedented domestic market but by a sudden and drastic upswing in estimates of military and governmental requirements. Additionally, oil exports are running far below the volume requested, amounting to less than forty percent in a recent quarter, and export licenses are reportedly being approved on the basis of urgent need *only. AX recent White House release sees little likelihood that estimated requirements of the sixteen nations participating in the proposed Marshall Plan can be met in full over its projected life—1948 to 1951. Present demand dictates maintenance of refinery operations at the highest possible level and the Bureau of Mines has forecast daily average crude runs in 1948 of 5,265,000 bbl. The Economics Advisory Committee of the Interstate Oil Compact Commission recently estimated the 1948 demand for petroleum products at nearly 6 pct above 1947. They further estimate daily average crude runs of 5,375,000 bbl in 1948, some 2 pct higher than forecast by the Bureau of Mines. Projected demand exceeds supply to the extent that Capitol Hill is reportedly investigating ways of enabling oil companies to act in concert without danger of antitrust prosecution, such as elimination of crosshauls, pooling of products, and lowering of octane.

Jan 1, 1948

By Walter Miller

Crude oil stocks were some 10,000,000 bbl higher on June I, 1947, than at any time during 1946 but the extremely heavy refinery runs the last half of 1947 cut crude inventories to approximately the 1946 closing level of 225,000,000 bbl. Many refiners were seriously short of crude oil during the year. This shortage was reflected in numerous advances in the posted price of crude, justified in part as an incentive for more production but more generally due to competitive bidding. Some purchasers of crude, endeavoring to keep their plants running, resorted to the payment, either directly or indirectly, of premiums above the posted price. Another common practice employed by some suppliers of crude oil was to demand refined products in exchange or trade for their raw material. The refined products picture has darkened in spite of record throughputs. Stocks of gasoline and light and heavy fuel oils were uncomfortably low at the beginning of the year and were in general still lower at the close. The rationing of some products, principally gasoline, to dealers and stations? initiated during the year, gained momentum as stocks continued to diminish. The emphasis placed by the manufacturers of oil-burning equipment on the convenience and economy of heating with oil, together with the tight situation in coal, has developed a tremendous demand for burning oils. Consumption of liquefied petroleum gas for domestic and household fuel had more than doubled in 1946 over 1943, and the demand seems to be limited only by the ability of the equipment builders to furnish necessary storage. transportation, and burning equipment. The supply situation is likely to become more acute in 1948. Demand for petroleum products is being pushed to new heights not only by the unprecedented domestic market but by a sudden and drastic upswing in estimates of military and governmental requirements. Additionally, oil exports are running far below the volume requested, amounting to less than forty percent in a recent quarter, and export licenses are reportedly being approved on the basis of urgent need *only. AX recent White House release sees little likelihood that estimated requirements of the sixteen nations participating in the proposed Marshall Plan can be met in full over its projected life—1948 to 1951. Present demand dictates maintenance of refinery operations at the highest possible level and the Bureau of Mines has forecast daily average crude runs in 1948 of 5,265,000 bbl. The Economics Advisory Committee of the Interstate Oil Compact Commission recently estimated the 1948 demand for petroleum products at nearly 6 pct above 1947. They further estimate daily average crude runs of 5,375,000 bbl in 1948, some 2 pct higher than forecast by the Bureau of Mines. Projected demand exceeds supply to the extent that Capitol Hill is reportedly investigating ways of enabling oil companies to act in concert without danger of antitrust prosecution, such as elimination of crosshauls, pooling of products, and lowering of octane.

Jan 1, 1948

By Charles W. Carter, Alfred H. Bell

In 1943, Illinois produced 82,256,000 bbl. of oil, or 5.5 per cent of the total for the United States, and ranked sixth in the nation in oil production. This represents a decline of 23 per cent from 1942, when the total Illinois production was 106,ggo,o~~ bbl. and Illinois ranked fifth. The daily average production for 1943 was approximately 225,000 bbl. Daily averages by months were as follows: Jan......... 238,000 July......... 218,000 Feb......... 240,000 Aug......... 216,000 Mar......... 237,qoo Sept........ 220,ooo Apr......... 230,000 Oct......... 220,000 May....... 221,000 Nov......... 223,000 June......; . 222,000 Dec......... z18,ooo This shows that most of the decline during the year took place between March and May, and that for the last eight months of 1943 production has been essentially steady. This means that there has been enough production from new wells drilled to balance the natural decline of the Older wells. The trends of drilling and production are shown in Fig. I and Table 3.

Jan 1, 1944

By Alfred H. Bell, Charles W. Carter

In 1943, Illinois produced 82,256,000 bbl. of oil, or 5.5 per cent of the total for the United States, and ranked sixth in the nation in oil production. This represents a decline of 23 per cent from 1942, when the total Illinois production was 106,ggo,o~~ bbl. and Illinois ranked fifth. The daily average production for 1943 was approximately 225,000 bbl. Daily averages by months were as follows: Jan......... 238,000 July......... 218,000 Feb......... 240,000 Aug......... 216,000 Mar......... 237,qoo Sept........ 220,ooo Apr......... 230,000 Oct......... 220,000 May....... 221,000 Nov......... 223,000 June......; . 222,000 Dec......... z18,ooo This shows that most of the decline during the year took place between March and May, and that for the last eight months of 1943 production has been essentially steady. This means that there has been enough production from new wells drilled to balance the natural decline of the Older wells. The trends of drilling and production are shown in Fig. I and Table 3.

Jan 1, 1944

By Paul Hunt

UP to June, 1923, the Park-Utah mine had shipped about 94,000 tons of a direet-smelting ore of a gross value of $4,200,000, or about $45. a ton. These values were in gold and silver only, although the ore carried small amounts of lead, copper and zinc. Freight, treatment and deductions had averaged $15.40 a ton. At the expiration of the Pittman Silver Act there was in sight about 30,000 tons of a similar ore with a gross value of about $15 a ton in gold and silver, and a large body of partly developed lead-zinc ore of a gross value of about $20 a ton, 40 per cent. of which was represented by the lead-zinc content and the balance by the silver and gold. Mine costs had been high during the life of the Pittman Act, but as a large part of the profits had gone into equipment of the mine and the orebodies were large and had good walls, we knew that mine costs could be greatly reduced. We were therefore faced by the necessity of getting lower freight and smelter rates or of concentrating the ore. We did obtain better freight rates on lower grade ore, and a favorable smelting rate on the small tonnage of siliccous silver-gold ore, but this smelter rate could not be applied to the lead-zinc ore with any profit to ourselves. The Judge mill of the Park City Mining & Smelting Co., with which we were affiliated, was running to capacity; if we built our own mill it ineant a 5-mile freight haul to a satisfactory millsite and a year's delay. Fortunately, the International Sillelting Co. had just inherited a mill at Tooele which, with some changes, was about double the catpscity required for its own ores. Flotation tests were run on Park-Utah ore and a contract entered into with a low base treatment charge per ton, the tariff being largely fixed by the metallurgical deductions. This contract has been admirably calculated so that the miner can follow a lean orenbody to its limit. Such a procedure has no doubt made it difficult for the smelting company at times, but it has resulted in finding ore extensions that otherwise might have been missed, so In the long run it has profited too. A flat rate per ton would have been like mining up to the claim endlines in a great many of the stopes. In order to offer such a contract it can be inferred that the smelting company must have been able to make high reeoveries and high-grade products on a very lean ore.

Jan 1, 1928

By John C. Branner

Inquiries are frequently made concerning the chalk- and clay-beds of Arkansas, usually with a view to the manufacture of Portland cement. The chalk-deposits were first described by Professor R. T. Hill in the annual report of the Geological Survey of Arkansas for 1888, vol. ii., pp. 153-162. Since the publication of that report I have visited localities then unknown, and have accumulated considerable additional information concerning these deposits, dl of which is brought together in the present paper. My report upon the clays of the State has never been published; only a few of the more conveniently available deposits are mentioned in the present paper. The Chalk-Deposits. Stratigraphic Position of the Chalk.—The chalk-deposits of Arkansas belong to rocks of Cretaceous age. The Cretaceous rocks are confined to a single definite area in Southwest Arkansas. Beginning on the Ouachita river, a little northeast of Arkadelphia, its southern or upper margin follows a line about five miles southeast of, and approximately parallel to, the St. Louis, Iron Mountain and Southern Railway from Arkadelphia

Jan 1, 1898

By Benj. Lazer

Multiple seam mining has been studied and writ- ten about extensively in the past and in the latest review of the subject in 1956 David Stemple covered it exhaustively. The present discussion has to do with only one phase of the problem-"The effects on upper seams when the lower seams have been mined first." The study presented here is based on observations made in mining operations in southern West Virginia and adjoining areas of Virginia and Kentucky during the past 43 years. These observations are largely confined to the Pocahontas coalfields of southern West Virginia which have, since 1883, produced well over one billion tons of coal from an area of about 300 sq miles and where multiple seam mining has been active, or is now active, at more than 40 operations. The observations and conclusions as to the effects on upper seams when lower seams have previously been mined are therefore related only to the local coalfields in the area of the three states named but I believe that they can be applied generally to other coalfields.

Jan 9, 1965

By Michel L. Bilodeau

The objective of delineation drilling is to provide a data base for the tonnage and grade estimates required to evaluate the economics of mine development. As drilling information is accumulated, geological risk is reduced and more reliable estimates of tonnage and grade are obtained. Investment in drilling is justified by the benefits which result from improving the reliability of the economic criteria evaluated. These benefits are subject to diminishing returns, i.e. as drilling information is accumulated the reliability of the economic criteria evaluated is improved but at a decreasing rate. At the same time, costs are incurred -- the direct investment cost associated with additional drilling and the time cost of delaying possible production revenues. The economic sampling limit is de- fined by the point at which the marginal benefits from drilling investment just balance the marginal costs. The paper describes the formulation of an economic model to optimize investment in delineation drilling. The model is applied to a simulated mineral deposit to illustrate the economic effects of a sequential drilling program.

Jan 1, 1977

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

[Note.—The paper of Mr. Hoffman on " Practical Results in the Magnetic Concentration of Iron-Ore " (page 602); that of Mr. Langdon on "The Use of Magnetic Concentrates in the Port Henry Blast-Furnaaces" (page 599); and those of Mr. Landis on "The Determination of Iron in the Tails from Magnetic Concentration " (page 609) and "Note on Sampling Iron-Ore" (page 611), were all prepared as contributions to this discussion.] The papers of Mr. Langdon and Mr. Hoffman were presented. W. H. Hoffman, Croton Mines, N. Y.: I will add a few remarks, by way of answer to inquiries for further details. The Croton Mines are particularly well located for cheap mining. The ore-bed is very large, and so lies in relation to the railway tracks of the Harlem and other railroads that a very large proportion of our mining for several years to come can be done above these tracks. The concentrating-mill is now 400 feet from where we are working in the quarry. In blasting we never remove less than 2500 tons at a blast,

Jan 1, 1892

Arthur H. Elliott, New York, N. Y.: We have all been very much interested in the results of Dr. Bone's work, which Mr. Ellis has presented to us this evening. The high temperatures attained by this method perhaps afford us an explanation of the temperatures reached in the puddling-furnace with its crude and almost primitive methods of burning fuel, by means of which we have, nevertheless, been able to melt iron in a comparatively short time, and keep it in a molten condition down to a high degree of purity. No doubt many of us have wondered, as I have done, how such a result could be obtained in such a way; and it occurs to me that, perhaps, Dr. Bone has supplied the explanation in disclosing the effect on combustion of burning gas and air after passing through, and in contact with, a porous refractory body. May not the fettling of the puddling-furnace have, in some degree, an effect upon the combustion like the influence of the porous diaphragm employed by Dr. Bone ?

Jan 1, 1913

By James Elton

THIS paper covers, besides laboratory work, a study of actual operation at the Washoe Smelter over a considerable period of time, together with the results of a visit to the Midvale plant of the United States Smelting- & Refining Co., near Salt Lake. For the latter privilege, as well as permission to publish the resulting data herein given, I am indebted to George W. Heintz, General Manager of the Midvale plant, and here take pleasure in. expressing my appreciation for the many courtesies extended to me by Mr. Heintz and members of the technical staff at the smelter. Almost all of the world's supply of arsenic is recovered as a by-product in the smelting of other metals. It is seen on the market in various forms, the most common being arsenic trioxide, the ? white arsenic " of commerce, which is sold as a heavy white powder, or in white, glassy, translucent masses. The trioxide is used in the manufacture of pigment, glass, and insecticides. About 50 per cent. of the domestic consumption is supplied by imports.

Jan 8, 1913

By F. J. Zuiderweg, G. G. Bemer

Results of a study aimed at assessing kinetics and mechanisms of the batch agglomeration process in suspension are discussed. A recently developed light backscatter technique which enables the increase of average particle size from 1 to 5000 µm to be followed, was used to determine agglomeration kinetics. Growth curves and agglomerate size distributions were obtained in a stirred vessel for various model systems and operating conditions. Four distinct growth regimes were identified, i. e. the flocculation regime, the zero-growth regime, the fast growth regime, and the equilibrium regime. Further, it was observed that large differences in the occurrence and duration of these regimes resulted from small variations in parameters, such as size distribution of the initial particles and the binding-liquid to solid ratio. Mechanisms that determine the occurrence of the relevant regimes are discussed. The growth process was described in terms of population balance equations. In this way, the growth rate, the equilibrium agglomerate size distribution, and the evolution of the agglomerate size distribution were generated. The agreement with experimental results is satisfactory.

Jan 1, 1980

By C. W. Bildt

During many years of service in the iron and steel industry I have frequently found, as have also many other engineers, that the common devices used for feeding coal into gas-producers are not what they ought to be in order to secure the best economy. The hopper-and-cone so generally used is familiar to all, and a brief study of its action will surely satisfy everybody that this device has several serious faults. In the first place, the charging is intermittent, and depends entirely upon an attendant. When the hopper is frequently emptied, it may work fairly well, but even then it suddeinly discharges into the hot producers a large body of coal, which is often violently converted into gas that rushes into the furnace, and, as the damper for the combustion-air cannot be regulated every time the producer is charged, there will be an excess of gas, which goes up the chimney unburned. Between the chargings the quantity of gas generated decreases, and there will often be an excess of air in the furnace,

Jan 1, 1899

By J. C. Bayles

An obstacle to the more careful and satisfactory study of metals has been the difficulty in harmonizing the results of chemical and physical tests. These give us records of observations made from different and often widely separate points of view, and while it is true that they furnish bases for more or less accurate triangulations into the realm of speculation, it is doubtful if, with only the laboratory and the testing machine, our investigations would not move in parallel lines, leaving between them an unexplored field in which must probably be sought the information which shall connect the results of chemical and physical tests, and give to both a practical value which neither has yet been found to possess. The use of the microscope in the study of metals is not a new thing, but it is only lately that it has begun to attract the attention it merits or to show results of tangible value to the metallurgist. Among recent valuable contributions to the literature of this subject, I have been especially interested in the work of Mr. A. Martens, of

Jan 1, 1883

By H. W. Morse

THE CHAIRMAN (H. W. MORSE).-Gentlemen, for the first time in the history of the American Institute of Mining Engineers, we have a full session on the subject of leaching-especially on the leaching of copper ores.. This branch of metallurgy is rather in its infancy. We have had one big plant running for a year or more, and pretty successfully; and another one which will be started in February or March, the New Cornelia. We have another one at Garfield for the Utah company, which is just designed and construction begun; and from several other points come reports of interesting test work. The first paper on the program this evening is one of some of the test work on the New Cornelia ore by myself and Mr. H. A. Tobelmann. LAWRENCE ADDICKS, New York, N. Y. (written discussion).-The Ajo proposition has had, as I understand it, two great advantages: it has not been obliged to measure leaching against flotation or some other metallurgical process, and it deals with a copper content high enough

Jan 12, 1916

By V. S. Gupt, W. H. Somerton

Rock may undergo great changes in physical properties when heated to high temperatures and then cooled, The temperature and intensity of reactions causing rock alterntiorl.s can he controlled by introducing certain chemicals during heat treament. Three typical outcrop sandsone samples were saturuted with common salt solutions, then heated to several maximum temperatures. After cooling, it was found that per-rrreuhilities had increased much more for salt-saturated samples than for samples not saturated with salt but heated to the same temperatures. This was only true, however. for samples heated above the melting points of the particrrlar salts. Potassium chloritle was particularly effective with Bandera sandstone. Samples saturated with potassium chlorirlr. solution and heated to 900C showed an 11-fold increa.se in perrrieahility. Samples without potasrirdrn chloritle but heated to the .same temperature. showed only a 2.7-jold incresre in permecahility. In application, it seems possible that injecting chemicalc into the formations from a wellbore followed by applying intensive borehole heating might promote reactions which would greatly improve permeability of the formalions. INTRODUCTION Great changes in the physical properties of rocks which have been heated to temperatures in the range of 600 to 800C have been reported earlier. Permeability increases of 50 per cent, and equivalent decreases in sonic velocity and breaking strength have been observed. Although there might be some suppression of certain reactions responsiblc for these changes when rock samples are heated under simulated reservoir pressure conditions. recent work has shown that these are more than offset by the increased importance of other reactions at high pressures. The reactions considered responsible for alteration of rock properties by heating include differential thermal expansion. dehydration, phase changes and dissociation of mineral constituents. Ceramists have long known that temperatures at which reactions occur can be raised or lowered by the presence of certain impurities in the sys. tcnl. Thus the possibility exists that by saturating rocks with appropriate solutions. desired reactions might be accelerated and unwanted reactions might be suppressec! when the rock is heated. Purpose of the present work was to investigate the effects of several common salts on the thermal alteration of sandstones. Types of reactions which might occur are reviewed and the findings of a number of thernlochemical alteration tests are presented. THEKMOCHEMICAL ALTERATION OF SANDSTONE MINERALS The most abundant constituent of most sandstones is quartz. Quartz can exist in at least eight different forms, but in the temperature range of immediate interest (to 900C) only two forms are of importance—alpha quartz below 573C and beta quartz above this temperature. Although the alpha-beta inversion of quartz is very important in thermal alteration of rocks. it is not particularly important here because the inversion temperature cannot be changed significantly by the presence of impurities or by the application of pressure. The transition temperature of quartz to tridynlite is 867C. but the transition is very sluggish. Tridymite is considered to be a metastable transition phase between two stable phases: quartz?cristobalite. However. the transition temperature for tridymite to cristobalite is 1,470C.4 The quartz-tridymite-cristobalite transition can be accelerated substantially by the presence of fluxing agents. Finely divided calcium, magnesium and titanium oxides accelerate the conversion while A12O may retard it. A Mixture of NaCl and CsCl reduces the temperature for cristobalite formation by as much as 420°C. Feldspars constitute the second most important mineral in sandstones. The melting points of feldspars range between 1,000 and 1,700°C depending upon the variety. No information available indicated any important role of fluxing agents in the thermal alteration of this group of minerals. Carbonate minerals are subject to dissociation at temperatures within the range of the present investigation. The dissociation of magnesite can start at a temperature of 373°C, but the reaction is sluggish and might not occur untll a temperature of 500°C or ,higher is reached. Dolomite dissociates in two stages at 500°C and 890°C, whereas calcite dissociation temperature is about 885C. Because CO2 is released in the dissociation of carbonates, ail such reactions are somewhat dependent upon CO2 partial pressure. In the absence of CO: in the surrounding atmosphere, the dissociation of calcite starts at 500°C.However. when 1 atm of CO surrounds the sample, the dissociation does not start until 900C. The other carbonates are apparently much less sensitive to a change in partial pressure of CO2. The aragonite calcite transformation can occur an!. where within the temperature range of 357 to 488°C. depending upon the presence of impurities such as barium. strontium. lead and perhaps zinc. The differential thermal analysis (DTA) curves of both magnesitc and dolomite vary with the presence of 'impuritics. The presence of iron in particular seems to affect the magnesitc DTA curve

Jan 1, 1966