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By D. M. S. Bhatia, Richard D. Hagni

Five sulfide minerals from the Magmont mine, southeast Missouri were sampled for 31 trace elements in over 300 samples by laser microprobe spectrographic analysis of polished sections. The concentration of several trace elements shows a pattern of progressive variation with depth (space) and variation with different paragenetic stages (time) of each mineral. Factor analysis of the geochemical data shows sympathetic correlation both in space and in time of Bi, Cd, Ge, and Sn in galena and sphalerite, and Ni and Co in sphalerite and marcasite.

Jan 1, 1981

By John Norton

IN spite of the very general employment of nitride hardening, there is still considerable doubt as to the real nature of the mechanism involved. Experience has shown that the addition of small amounts of hardening elements to iron or steel results in a wide variety of desirable properties in a nitrided case. Perhaps the foremost of these elements is aluminum and in this investigation an attempt has been made to study the behavior of aluminum during the hardening process. It is believed that the establishment of a complete atomic picture of the metal at various stages of the process will indicate the relationships between the several kinds of atoms and their individual influences on the physical properties in a clear and direct fashion. A consideration of the problem suggests a surprising similarity between the mechanisms of nitride hardening and of age-hardening. It is now generally understood that age-hardening may take place by one of two distinct processes, the first involving the precipitation of a finely dispersed phase and the other being concerned with the modifica-tion of an existing phase. Following much the same line of reasoning, two theories of nitride hardening have been suggested. The first expla-nation, which has been generally discussed, particularly by Fry,1 states in brief that the presence of aluminum causes the precipitation of alumi-num nitride during nitriding and that this finely dispersed phase is the primary cause of hardening. The second explanation, which has not been published but which has been freely discussed by those interested in the problem, postulates the substitution of aluminum atoms for certain of the iron atoms in the several iron-nitrogen phases in the same manner that the substitutional iron-aluminum solid solution is formed. The marked increase in hardness, as compared with the aluminum-free

Jan 1, 1934

By C. M. White

CITIZENSHIP is a rather abstract subject on which a great deal could be said-a subject on which a great deal is said -and still one which too many of us seldom think about and seldom work at. Too many of us engineers and business men have but a vague idea of citizenship. We think that if we go to the polls on election day and obey the laws scrupulously, with the exception of an occasional traffic violation, we are pretty good citizens and are doing our duty by our city, state, and nation. But when you think it over, that's a very passive observance of the important right of counting oneself a citizen of a country. There is nothing very positive in that attitude. There is nothing that indicates that we have sufficient interest to really go out and do a job for the -welfare of our country, forgetting any personal advantages or inconveniences that might arise. In other words, this type of voting-on-election- day, law-abiding citizenship does not keep us awake a single minute; it does not take any particular thought or require the expenditure of any time or energy.

Jan 1, 1939

By W. M. Pierce

CORRUGATED sheet zinc has been used abroad for a great many years as a roofing material. In this country it has been in use for about 10 years. From the outset it was recognized that zinc sheets required closer spacing of the supporting purlins than steel sheets. Exact data regarding safe maximum fiber stresses were not available, however, and on occasions the span used was excessive and the sheets sagged. This paper describes both service and laboratory tests to determine safe maximum fiber-stress values for various grades of zinc for use in calculating the proper purlin spacings for any gage and profile under given loading conditions. These tests consist of laboratory loading tests on full-size roof sections over extended periods of time; of actual roof installations erected in conformity with the indications of the laboratory tests and observed over a period of years; of careful determinations of the apparent elastic limit of several grades of zinc, and finally of static tests1 (so-called creep tests) to determine the rate of flow of zinc under a variety of static tensile stresses at definite temperatures. Certain of the individual tests extended over a period of more than two years.

Jan 1, 1929

By Charles M. Brown, Russell Franks, W. O. Binder

Occasionally in the application of the austenitic chromium-nickel steels to corrosive conditions, failures have occurred by cracking without serious general over-all attack of the metal. As pointed out by Foyt and Scheil(1),2 and by Scheil, et al.(2) as well as by Hodge and Miller(3), the stress-corrosion failures that have occurred have been limited in number, and have taken place only when the steels were exposed to certain corrodents. These investigators have stated that while stress- corrosion cracking can be intergranular in nature and originate at the grain boundaries of the austenitic chromium-nickel steels, it can also take place in trans- granular fashion. They have shown that the cracking may be either initiated at the grain boundaries and may propagate along grain boundaries for some distance and then suddenly extend across grains, or it may begin in a transgranular fashion and suddenly proceed along grain boundaries until the cracking stops. Their data further show that when austenitic stainless steel is subject to intergranular attack, stress will concentrate and cause cracking in service. These investigators have studied the effect of the metals titanium and columbium which are added to the steels to impart immunity to intergranular attack, and molybdenum which is added to improve resistance to general corrosion.

Jan 1, 1945

By D. B. Hobbs, L. W. Kempf, R. S. Archer

Silicon is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13 per cent. of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 25S, Special 17s and 51s of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both 'normal" and "modified" sand castings. Review of Literature The literature on the heat treatment of aluminum-silicon alloys is not very extensive. The following review gives the principal references of which the authors are aware, in which appreciable information may be found.

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1951

By Charles Will Wright

FRANCE will be given a large portion of the Marshall Plan funds for relief, reconstruction, and industrial development in France and in her colonial possessions. At present that country is not in position to export any large tonnages of the mineral products needed in the United States. However, if, through Marshall Plan aid and private capital investment, production of these products can be largely increased, agreement should be made by which the United States is to get a substantial portion of such increased output in part payment for the material and technical aid they receive. France issued a decree, published in the "Official Gazette" on Feb. 3, 1948, which permits conversion into dollars of dividends derived from dollar investment in Government-approved projects and will agree to a scale of capital amortization to be determined in each individual case. This decree is to encourage private capital to cooperate with local capital in industrial undertakings. The French Colonial Ministry has prepared an extensive program for aid to the mining industries in overseas possessions to be undertaken by

Jan 1, 1948

By A. H. Miller

TEMPERATURE considerations are of prime importance in the manufacture of steel products-front the time the metal is produced in the melting furnace, where the chemical reactions have a direct dependence on the temperatures of the bath, to the final machining of work on which the expansion due to the rise in temperature of the forgings during machining must be allowed for. Methods employed and difficulties encountered in some of the more important steps are here outlined. These methods are the result of years of experience, with many methods of temperature determination, and have been successful in routine works practice in the manufacture of high-quality steels. In the operations of melting, forging, and heat treatment, if the product is to be of the best quality each operation must be carefully followed through. A high-quality product cannot be obtained even with the best heat treatment if the steel is poorly melted, and, conversely, the best steel ever made may he spoiled by inefficient heat treatment. To perform the best work in any of these operations, temperatures must be accurately regulated.

Jan 8, 1919

By F. Osmond

When a metal (whether a simple substance, an alloy, or a compound) presents, in each of the smallest parts to which it can be redueed by mechanical division, a constant chemical composition, it is defined as chemically homogeneous. But chemical hombgeneity by no means necessitates mechanical homogeneity. There are no perfectly amorphous metals. Crystalline forces, on the one hand, and tensions or compressions, on the other band, determined by icequalities of temperature in the mass during heating or cooling, give rise in every metal to the formation of geometric elements of structure. These elements may, moreover, assume perfect crystalline forms, with their planes of cleavage; or embryonic crystalline forms, segregated in the midst of. a paste of confused organization; or pseudo-crystalline forms of expansion and contraction, like those produced in the drying of gelatinous precipitates or (most frequently) these different forms associated. 111 either case the adhesions between two adjoining structural elements, respectively homogeneous, may be very different from the interior cohesion of each of these elements. The mechanical properties of this complex aggregate cannot be simple, and, when it is submitted to strains sufficient to produce deformation, the results may be very different according to the type of structure or the manner in which it is affected by the strains. It may be fairly said that a metal does not present a single resistance to tension, or a single resistance to compression, etc., but in fact, at least theoretically, as many resistances to tension, compression, etc., as it may possess coexistent features of structure; only, in any single test, it is the weakest of the resistances involved which makes itself evident. For further explanation, let us imagine a cylinder A B (Fig. I), formed of two similar halves A and B, placed together upon their common base x y. Such a system evidently presents no resistance to axial tension, while it would resist axial compression like a single

Jan 1, 1894

Executive JVW REYNOLDS, Chairman SYDNEY H BALL E DEGOLYER WILLIAM H BASSETT SAMUEL A TAYLOR Finance GEORGE D BARRON, Chairman H A GUESS GEORGE OTIS SMITH Membership ] H CALLOW, Chairman GEORGE D BARRON WILBER JUDSON JOHN A CHURCH, JR H N SPICER Alternates LEWIS W FRANCIS LOUIS D HUNTOON F T RUBIDGE

Jan 1, 1923

By G. E. Agar, A. L. Mular

G. E. Agar (Manager, Minerals Processing Research, International Minerals & Chemical Corp., Skokie, III.) — The author notes a discrepancy between the parameters a and ß which are the slopes of the size distribution and energy-size modulus plots respectively. The reason for the discrepancy and the systematic decrease in the magnitude of a with grinding time is abundantly clear from the work of Fuerstenau8 on dry grinding. Fuerstenau shows very clearly in his Fig. 5 that at short retention times the parameter a is the same as that obtained by sizing over the complete size range. From this figure, it is obvious that sizing to only 400 mesh gave distribution curves similar to Mular's - that is, the slope apparently decreased systematically with increased grinding. As a consequence of the improper determination of a, the magnitude of ß given by Mular must be larger than the true value. In order to demonstrate this, the following Fig. 6 was taken from Mular's paper (his Fig. 1). Fuer-stenau's results show that we can approximate the correct value of K by drawing lines parallel to the short retention time curves through the 400-mesh

Jan 1, 1963

By Thomas Egleston

DURING the year 1873, my attention was called to the frequent accidents, resulting from the breaking of rails, on the different railroads in this' country, and I was requested to investigate the subject. The plan of investigation I proposed was to ascertain, in as many cases as possible, the exact hist* of broken rails, both in this country and in Europe; to collect information in Europe relating to the tests which rails used there were required to undergo, and to experiment upon the pieces of rails broken on the road, with a view to ascertain whether their fracture was due to their chemical constitution, bad manufacture, to a reduction in strength owing to temperature, or to physical changes in the constitution of the rail. The investigation was commenced by the collection of statistics, and for this purpose I spent several months in Europe, collecting information on the subject of broken rails, as well as the life of iron and steel rails generally, and inquiring into the systems of purchasing and of testing them employed by the railroads there, intending, on my return, to make a series of analyses of rails broken, both in this country and in Europe; to ascertain, if possible, how far great cold had an influence on the fracture; to examine whether the rail broken, either on the road or afterwards, underwent, at or about the fracture, any physical change, and to make a series of experiments on the strength of rails manufactured in the United States or sold in the American market. Unfortunately, the panic of 1873 came on, just before my return from Europe, and prevented the carrying out of the larger part of the plan proposed; as, however, I had collected in the meantime, a large number of statistics of different kinds from all parts of Europe, and had made a number of interesting experiments and investigations, I have thought it would be worth while to communicate some

By T. Egleston

DURING the year 1873, my attention was called to the frequent accidents, resulting from the breaking of rails, on the different railroads in this country, and I was requested to investigate the subject. The plan of investigation I proposed was to ascertain, in as many cases as possible, the exact history of broken rails, both in this country and in Europe; to collect information in Europe relating to the tests which rails used there were required to undergo, and to experiment upon the pieces of rails broken on the road, with a view to ascertain whether their fracture was due to their chemical constitution, bad manufacture, to a reduction in strength owing to temperature, or to physical changes in the constitution of the rail. The investigation was commenced by the collection of statistics, and for this purpose I spent several months in Europe, collecting information on the subject of broken rails, as well as the life of iron and steel rails generally, and inquiring into the systems of purchasing and of testing them employed by the railroads there, intending, on my return, to make a series of analyses of rails broken, both in this country and in Europe; to ascertain, if possible, how far great cold had an influence on the fracture ; to examine whether the rail broken, either on the road or afterwards, underwent, at or about the fracture, any physical change, and to make a series of experiments on the strength of rails manufactured in the United States or sold in the American market. Unfortunately, the panic of 1873 came on, just before my return from Europe, and prevented the carrying out of the larger part of the plan proposed ; as, however, I had collected in the meantime, a large number of statistics of different kinds from all parts of Europe, and had made a number of interesting experiments and investigations, I have thought it would be worth while to communicate some

Jan 1, 1875

By Persifor Frazer

The structure of the Caucasus as made out by the Russian geologists and represented in Pamphlet XXII. of the Livret Guide, by Loewinson-Lessing, is an overturned anticlillal from Lars to Passanour; a distorted synclinal with monoclinal dip from Passanour to near the summit of the anti-Caucasus chain south of Tiflis; and another overturned auticlinal from this point to Erivan on the Armenian border. Ng—Neogene; Pg— Paleogene ; J,—Upper Junssic (and Cretaceolls in other parts of the chain) ; J1—Lias ; Pz—Paleozoic schists plicated ; yd—massives of granite and diabase; —porphyries ; —trachytes, andesites; Pz, Mz, plicated sedimentary deposits of Armenia. The details of the geology, however, are extremely complicated—so much so, indeed, as to make it impossible for any set of men to have worked them out in a single season. For 'the structure as a whole it will be necessary, therefore, to rely implicitly upon the labors of the Russian Geological Survey, and it is intended here only to state these, and to record a few notes supplementing them. Setting out from Wladikavkaz in the early morning, we pass

Jan 1, 1899

By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.'-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.' The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.' Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low' used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

By T. Glen Heslop, Dennis H. Laubscher

INTRODUCTION In all cave mining operations waste is drawn mixed in the ore, hauled, hoisted and milled. This waste usually contains some mineral which partly covers some of the costs of mining and milling it, but it still re- presents a loss of profits as the production rate from the mine is matched to the mill capacity - every tonne of waste milled replaces a tonne of profitable ore. Draw control aims to reduce the amount of waste drawn and to increase the amount of ore recovered. It is also used to regulate the grade of ore flowing to the mill and in block cave blocks to prevent potential stress build- up on the major apexes above grizzly drifts. This paper summarises what has been learnt about draw control in the forty years that cave mining methods have been used in the three largest underground chrysotile asbestos mines in the southern hemisphere. The four mining methods to which draw control has been applied are: a. Block caving. b. Shrinkage with overburden caving. c. Sublevel caving. d. Open stoping. Open stoping has been included because on a number of occasions severe falls from the back and side of these open stopes have occurred. Without full records of where and when ore is blasted, when and how much ore has been drawn from each of the drawpoints, it would be impossible to analyse the migration of ore and fallen waste in the stope. Several problems peculiar to chrysotile asbestos ore bodies affect the practice of draw control. Heterogeneous fragmentation, cavities, side pressures and the interaction of stresses in the caved ore affect the migration of ore under draw. Fibre is normally not developed uniformly throughout the ore bodies, values vary from place to place but there is usually a general decrease upwards and the hangingwall contact is an economic limit. The immediate hangingwall rock frequently looks like the ore body hostrock and is difficult to recognise in a drawpoint, and cannot be used as the marker for stopping draw. During caving or shrinkage, a large proportion of fibre becomes detached from the host rock and re- ports in the fines, which migrate differently to the larger rocks. The fines are not sticky, and flow easily if loose and dry, but compacted, the fibre and rock fines con- solidate the ore. During draw the proportion of fines in the ore varies considerably, as fines either flow relatively freely between the large rocks or become trapped and compacted above large rocks or hangups. This creates a large sampling error in drawpoint grade assessments, whether done visually or by bulk sampling, unless the assessments are done frequently. The method of draw control used is to regulate the draw rate in an attempt to lower the ore-waste interface as evenly as possible, and to finally stop working the drawpoint when a calculated tonnage has been drawn.

Jan 1, 1981

By J. S. Lasater

Resu1ts of experinmental measurernents of heat capacities and thermal conductivities of some typical porous rocks are presented. Measured heat capacities agree closely with va1ues calculated front known chenlical . compositions of the rocks. On the basis of this agreement, heat capacitir.7 of fluid-satttrated rocks were calc~ililted. Therrnal conductivities of the rock samples were measured under varioits conditions of fluid saturation. From these data therrnal dif-fvsivities were calculated. A significant variation of thermal diflusivity with trnlperature is indicated. Knowledge of the thermal characteristics of fluid-bearing porous rocks has become increasingly important with the development of thermal oil-recovery processes. Reliable thermal data for petroleum reservoir rocks are not available and approximate values are generally assumed for reservoir calculations. 'The effects of temperature, pressure and fluid saturation on thermal properties of porous rocks have not been carefully studied. The purpose of the present work was to measure and report the thermal characteristics of some typical porous rocks. A group of eight sedimentary rock samples, including limestone, shale, sandstone and silt-stone, was selected for the study. Properties reported include heat capacities, thermal conductivities and thermal diffusivities. The effect of fluid saturation on these properties was also considered. Determinations of thermal properties require precise measurements which are time consuming and difficult to reduce to a routine basis. Methods have not been developed for measurement of thermal proper-ties under conditions of pressure, temperature, and fluid saturation, which may be encountered in thermal recovery processes. As one approach to these problems, some preliminary work on methods of estimating thermal properties from other more readily measurable characteristics of the rock-fluid system is reported. The samples selected for the studies were oilfield cores from within, or closely associated with oil-productive zones. Descriptions of individual samples are given in Table 1. Clay minerals present in the samples were determined by differential thermal analysis (DTA). Quartz content was estimated from DTA cooling curves. For all but the thermal conductivity tests, a representative 200-gm sample of each core was disaggregated, thoroughly extracted in diox-ane and oven dried at 100°C. The cleaned and dried sample was care- fully split into appropriate portions for the several tests. Chemical analyses of the samples were obtained to permit calculations of heat capacities by methods which are outlined later. Resuits of chenlical analyses are given in Table 2. Heat contents of the test samples were measured by a Runsen-type calorimeter. The heat content of the unknown sample is measured relative to the known heat content of platinum. The apparatus is referred to as a relative error type because of the comparative measurements, and has the advantage of canceling systematic errors. Experimental results are reproducible within 0.5 per cent. A temperature base of 298.16 K is taken for heat content measurements. Measurements were made at five temperatures (260, 440, 620, 800 and 980° F). It was necessary to preheal the sample above the maximum experimental temperature to eliminate volatile constituents. Assuming the weight loss on pre-heat, ing was mostly water, a correction to the observed heat content was made to account for the water originally present in the sample. This latter procedure was followed in the determination of calculated heat contents as will be described later. The apparatus and the method of measure-