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By D. J. Carney, R. L. Stephenson

M. O. Holowaty (Inland Steel Co., Chicago)—Messrs. Stephenson and Carney should be commended on the presentation of this very interesting paper. They have introduced new ideas on sampling of sinter and have thereby made a valuable contribution to the qualitative evaluation of sinter. The paper undoubtedly presents a novel approach to the problem of sinter sampling and this is to be regarded as its main value. Sampling of sinter from the pallets prior to the discharge is by no means new. This sampling procedure was used in the past by Philbrook; Hamilton and Ameen and others. The sampling basket used by the authors of this paper, however, permits one actually to obtain a good sample of the sintering mixture. The basket which can also be described as a removable pallet goes then through the entire process of sintering and thus offers a sample which is positively representative of the batch in question. The authors' method of evaluating physical properties of sinter seems to be not altogether clear, however. It is felt that the following points should be clarified: I—In the section describing the shatter test the authors state that a 5-lb sample was used in the actual tests. There is no mention of the initial size of sinter particles used and the method of obtaining this 5-lb sample from the sinter cake weighing about 100 to 120 lb. It is also surprising that the sample was dropped from a height of 3 ft instead of the conventionally used 6 ft. Unfortunately there is no mention of the number of drops to which the sample was subjected. 2—The tumbler test used by Messrs. Stephenson and Carney in testing the samples of iron ore sinter was performed in a standard ASTM coke tumbling drum. The drum measures 3 ft in diam and is equipped with two 3-in. lifter bars. The distance of fall in this testing drum is identical with the distance used in the previously described shatter test. The number of drops in the tumbling drum is approximately double the number of revolutions. The basic difference then between the drop-shatter test used by Stephenson and Carney and the tumbling test seems to be the number of drops to which the sample is subjected and the abrasive action to which the sinter particles are exposed in the rotating drum. In any case, the choice between the shatter test and the tumbler test seems to be only a matter of taste and convenience. 3—The authors of the paper state that "in order to insure getting results that were representative . . . the entire sample obtained by means of the sampling basket was used as the starting material for the tumbler test. If the sample broke in pieces, all the pieces were used regardless of their size." The initial size of the material is known to be a very important factor, influencing seriously the final size of the particles. This should be particularly important in case of hard sinters. It seems also very troublesome and inconvenient to charge 12-in. cubes of sinter weighing about 100 lb into the testing drum. This could be eliminated by taking a standard fraction of somewhat smaller particles.

Jan 1, 1954

By F. E. Bash

WHENEVER electric and open-hearth steel men discuss the relative advantages of their respective methods, the question of temperature is always discussed, so that this paper is written in the hope that definite data may settle some of the questions and encourage further investigations along these lilies. The writer has had the opportunity of taking the tapping temperatures of steel from electric furnaces of different sizes in various plants and from a number of open hearths handling the same kind of steel. All temperature measurements were made with the same disappearing-filament type optical pyrometer and the corrections for emissivity applied were those worked out by Burgess,1 which are 0.40 for steel streams and 0.65 for slag. The correction is applied by calculating the curve giving the relation between the true and apparent temperature in the following formula: Log E = CZ log e( 1 _ 1 x \T2 T1) in which E = emissivity; C2 = 14,500; e = base of Napierien logarithms; ? = wave-length of light used = 0.65/4; T2 = true temperature, in degrees absolute; T,1 apparent temperature, in degrees absolute. The curve showing the relation between true and apparent temperature for steel and slag arc given in Fig. 1. For the purpose of comparison of open-hearth and electric furnaces, there are given in Table 1 the tapping temperatures of two 25-ton Heroult electric furnaces and one 6-ton with one 50-ton acid, one 40-ton basic, and one 65-ton acid open-hearth furnace, all making nickel ordnance steel for guns. The two 25-ton Heroult electric furnaces were finishing steel refined by the triplex process and the 6-ton Heroult finished steel that was partly refined in an open hearth.. In this table, the tapping temperature and the temperature of the steel stream into the first ingot

Jan 9, 1919

A price list of publications of the Geological Survey, complete to May, 1931, and with separate monthly notices of publications to (late, will be sent upon application to The Director, United States Geological Survey, Washington, D. C. A leaflet is issued each month listing new publications; it will be sent upon application to the Director, as well as Circulars containing information about topographic maps. Book publications of the Survey include (1) Annual Reports, (2) Monographs, (3) Professional Papers, (4) Bulletins, (5) Water Supply Papers, (6) chapters and volumes of Mineral Resources of the United States, (7) Folios of the Geologic Atlas of the United States and the World Atlas of Commercial Geology, (8) Topographic Folios and Topographic Maps that bear descriptive texts. Monographs, Folios of the Geologic Atlas of the United States and the World Atlas of Commercial Geology, and Topographic Folios and Topographic Maps, are not distributed free. A publication of one of the other classes can be distributed free only until the end of the fiscal year following that in which it was issued. No person can obtain more than one free copy of the same publication, and general requests for free publications, such as all of any series or all on any subject, can not be granted. In ordering publications one is requested to give both the series designation, as Bulletin 738 or Professional Paper 122, and the title. Give full address, plainly written, including county. Prepayment is required and may he made by postal, or express money order payable to the official charged with the sale of the publications. requested, as indicated in the discussion of each classification following; or it may be made in cash-exact amount -at sender's risk. Postage stamps are not accepted in payment for publications.

Jan 1, 1933

By B. J. Klee

What is the economic basis for direct, continuous particle size measurement and control? First, precise grinding control is necessary to achieve and maintain a specified recovery and throughput. Second, throughput and recovery are direct functions of particle size-and these two factors control the economic performance of the ore concentration process. Third, only size-based control using a particle size and percent solids monitor (PSM) has achieved the necessary precise control. Recovery, throughput and cost can be accurately measured for various concentrator operating conditions if particle size is closely controlled. From such data the economic results of different particle size grind points can be analyzed. This will reveal the best combination of recovery and throughput to meet objectives established by financial management. Predictable, repeatable response to set-point selection is essential if the projected profitability of the mill is to be reached.

Jan 11, 1976

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By Scott Turner

OUR Institute, in its annual Directory, states the following: The purpose of each Technical Committee is to further the development of the special mineral industries in its field, chiefly through obtaining and discussing papers suitable for publication by the Institute. The proper field of the new Health and Safety in Mines Committee is judged to include the entire mining industry, and involves the multitude of health and safety problems arising in all kinds of mining operations. The mining industry in the United States has made much progress during recent years in reducing accidents. This advance has been widespread, and has been especially notable in the mining of iron ore. Yet the statistics of the U. S. Bureau of Mines, when compared with figures of the National Safety Council for other industries, show that mining still has a higher personal mishap rate than any other major industry in this country. In addition, studies of dollars-and-cents cost of casualty occurrences indicate that an important part of our mining cost, held by various authorities to be as much as 10 per cent of the total, is due to accidents.

Jan 1, 1933

By R. E. Crockett

MAGNETITE mining and milling in the Eastern States was at capacity during 1940, owing to the heavy industrial, defense, and war demand, coupled temporarily with the almost total stoppage of imports of foreign ores other than those under American ownership. In New York State the active mines were those operated by the Republic Steel Corp. at Mineville and Lyon Mountain. Republic's new concentrating mill at Port Henry, handling the Mineville ores, went into production about the first of April. Other large magnetite deposits in New York are currently being prospected and studied and may be under development in the near future. In New Jersey the Mt. Hope and

Jan 1, 1941

By C. K. Leith

CERTAIN ideas on iron and steel sanctions to follow originated in a series of conferences held under the joint auspices of the War Department and Brookings Institute in Washington last spring. The views presented may be regarded as those of substantial segments of the steel industry. In view of the fact that steelmaking capacity can be so quickly converted to the production of armament, any effective control must necessarily include the entire steel industry and not solely the parts devoted to the production of implements of war. It must also be exercised all the way from production and shipment of raw materials through their ultimate conversion into finished products and use. Control will be dis- cussed under two main headings: (I) control of raw materials at the source; (2) control of steel capacity within the Axis countries.

Jan 1, 1944

By P. K. Currie, J. V. Walters

Solution mining of magnesium salts (Carnallite and Bischofite) is taking place near Veendam, in the northeast Netherlands. The magnesium salts are used for the production of magnesia sinter, used as a base material for the manufacture of refractory bricks for furnaces. This paper gives, first, an introduction to the operational procedure followed in Veendam, with the emphasis on some of the unique aspects, and then discusses rock-mechanical aspects of the cavity behaviour. The creep behaviour of magnesium salts is described, and Finite Element calculations on cavity stability and potential surface subsidence are discussed.

Jan 1, 1985

Jan 1, 1881

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,' in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By SAMUEL GOMPERS

THE name engineer makes a very strong appeal to one who appreciates the mechanism underlying the fabric of our civilization. Engineers are scouts of civilization. We send them ahead into the lone 'places-the wilderness, the jungles, the great watery expanses, to build the highways necessary for civilized man. The engineers must deal with Nature, with that mysterious dynamic thing we call "force," with materials. It is their function to direct the human activity necessary to coordinate these forces and material in order to make them serve the needs and aspirations of men. Because of my high conception of the engineering profession I was glad to accept the invitation to address The American Society of Mechanical Engineers to voice my understanding of the possibilities of your work as engineers of industry, and to suggest what seems to me the responsibility of the-engineer to the whole modern industrial system.

Jan 1, 1921

R. V. Norris, Wilkes-Barre, Pa. (communication to the Secretary*):—Mr. Stow's paper presents a series of arguments, numbered from 1 to 18, concerning the relative merits of four systems of colliery-ventilation, designated by the author as " plain pressure-ventilation," " plain exhaust-ventilation," " obstructed pressure-ventilation," and " obstructed exhaust-ventilation." These arguments are subsequently compared by means of tables, in which an arbitrary numerical value is assigned to each, and which consequently serve no other purpose than that of showing his opinions and predilections, as indicated by his assignment of the said numerical values. In addition to this general summary, Mr. Stow intimates his preference for a fifth method of colliery-ventilation—namely, what he calls " alternating pressure-ventilation," which consists in the running of the fan at "pressure " during working-hours, and as an " exhaust" between shifts—a system which he proposes as, perhaps, new, yet which he thinks deserves recognition " as a standard form." This proposed " standard form " is not to be found in practice ; and I think it would be impracticable in gaseous mines of large extent, for the following reasons: 1. It takes considerable time to reverse the air-current in a large mine; and the reversal would involve a period of complete stoppage of ventilation, long enough to permit serious accumulations of gas. 2. In shaft- and slope-mines, at least, it is hardly practicable to have " every man out of the mine" during the night, and certainly impracticable to avoid keeping mules and horses inside. 3. The doors necessary to divide and direct the air-current are properly hung to open against the air-pressure; and, unless

Jan 1, 1910

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By Robert E. Hochscheid

The subject article appears in the February, 1978, edition of Mining Engineering, and on page 190 carries the statement, "As most operators know, in a Water-Only cyclone, ability to adjust the vortex finder is quite important due to the sensitivity of this type of operations to variance in feed conditions and having to take them apart to make this adjustment is always a nuisance." Our experience as a manufacturer and supplier of Water Only cyclones does not agree with the above statement, and we offer the following brief discussion. Our company finds that the sensitivity of the Water-Only cyclone is a function of the fineness of the coal being washed, with the sensitivity to vortex finder length being greatest for coals coarser than 3/4-in. and virtually insensitive to raw coal finer than 1 mm. For coals finer than 1 mm, we find that we can use the shortest standard vortex finder in either our 10- or 15- in. Water Only cyclone without exception. For coals 5/8-in. x 1 mm ceramic vortex finders of fixed length have been satisfactory in all cases following an initial testing period in which the length was determined. Coals coarser that 5/8-in. are more sensitive to the vortex finder length, and two installations handling coals coarser than 1-in. continued to experiment with vortex finders of various lengths long after the initial startup period. For coals of all sizes, final adjustment of product quality has been achieved by determining the optimum size of apex orifice, which is accessible and readily changed, if necessary. Comments above assume no unusual change in the coal being washed or the required quality of clean coal.

Jan 1, 1979

By Oliver Bowles, Carl A. Gnam

THE construction industry normally contributes extensively to the general economic welfare of all sections of the country. Billions of dollars are spent for materials and labor, and the success or failure of many business enterprises depends upon the volume of construction. The steel, aluminum, copper, cement, brick and tile, lime, gypsum, stone, sand and gravel, and several of the less prominent mineral industries are vitally concerned. Of great interest, therefore, is the accumulation of needed construction following the relative inactivity of the past five years, the recent moderate revival in building, and the prospect of a broader and more definite upturn. One may judge the magnitude of possible expenditure for construction by what has occurred in the past. The peak years were 1925 to 1928, inclusive, when the annual values of con- tracts awarded amounted to over six billion dollars. In marked contrast was the 1933 total of about 1% billion, the lowest level shown in the Federal Reserve Board Index, which goes back to 1919, and the more favorable 1935 figure of about 1.7 billion. An increase of nearly four billion over the 1935 volume would be necessary to equal the peak year 1928.

Jan 1, 1936

By G. D. Hobson, I. Mrosovsky

Material balance relationships for expansion-type reservoirs above the bubble point have been discussed in recent years by H. N. Hall and M. F. Hawkins, Jr. The former drew attention to the effects of rock compressibility, and the latter to the effects of the compressibility of any interstitial water. Hawkins derived a general relationship which took note of oil, water and rock compressibilities, and then by assuming first, the absence of interstitial water and secondly, no effects due to interstitial water or rock compressibility, obtained relationships symbolically of the same form as those previously derived directly by Hall. Hawkins defined his terms clearly, and noted an approximation, due to the omission of a term involving the product of two compressibilities, made in reaching his final equation. There is, however, possible ambiguity with regard to Hall's written definition of the oil production term. One interpretation would mean that the produced oil and initial oil-in-place, if both required as stock tank barrels, would be obtained by using different formation volume factors in the conversion in order to satisfy the conditions implicit in Hall's formulae. The other would involve an approximation which, if used, was not stated. In both Hall's and Hawkins' studies the effect of the approximation or inconsistency is very slight. Nevertheless, it may be justifiable to give a somewhat more consistent derivation, since the complexity of the final relationships is not thereby greatly increased. Let the initial pore volume be Vi and the volume after a pressure drop of Ap, V. Then V = V, (1 - ?p . cr), where c, is the rock compressibility expressed as change in pore volume/unit pore volume/unit pressure change, and is defined with the initial pressure as base. Suppose that the interstitial water saturation under the initial conditions is Sw. The total volume of interstitial water under those conditions will be ViSw. If the volume of the water after dropping the pressure by ?p is V., this will be given by Vw = ViSw (1 + ?p.c,w), the compressibility of the water being c, which is ex- pressed using the volume at the initial pressure as base. If Boi is the reservoir volume factor of the crude oil for the initial reservoir conditions, and B. the equivalent factor when the pressure has dropped by ?p, with N the initial amount of oil expressed as stock tank barrels. N.Boi = Vi - V,Sw If n is the amount of oil produced (in terms of stock tank barrels) as a result of the pressure drop ?p, the remaining subsurface volume of oil at the lower pressure will be Bw, and Bc can be related to the compressibi:ity of oil and the pressure drop, and if c, is the compressibility factor based on the initial conditions, The relationship derived by Hawkins was case to a standard at the lower pressure, while a term (Ap) had been dropped, because of its smallness arising from its dependence on the products of two compressibility factors. When there is no interstitial water and rock compressibility can be ignored, Eq. 1 reduces to:

Jan 1, 1957

By George C. Branner

STATE geological surveys have had an interesting development in this country. They first appeared more than a hundred years ago. The fact that they have persisted and are now an important part of most state governments indicates the basic need for state departments con-cerned with mineral problems. The number of state surveys in 1941 (43) is at an all-time high, as is the aggre¬gate appropriation for their support for the fiscal year 1940-'41 ($1,600,708). The first surveys, those of North and South Carolina (see Fig. 1), made their appearance in 1820-'30, but neither survived that period. During the next two decades surveys were created in twenty states, but only three survived. In fact, it was not until the decade 1900-'10, when eighteen surveys were created and only five abolished, that these agencies became firmly established.

Jan 1, 1941

By G. S. Cole, H. Biloni, G. F. Bolling

An experimental investigation of sovlze low .melting point alloys sJtows that a substvucture of isolated depressions can be the first manvestation of constitutional supercooling on solid-liquid interjaces veuealed by decanting. Electron-tni cvop vobe and wletallo gvaplic esanzinations, in tlze bulk belzind the interjace, oj the segregation associated with these isolated areas substantiate tlzei&apos;v depressed nature, since a solute of ko < 1 is enriched, and a solute of ko > 1 depleted. In contrast, the pox structuve, a set of projections often veported in the literature, leaves no trace oj. segvegation. These obserl;atims, accovlrpanied by a brief review of recent literature, point to inconsistencies between experirrental obsevvation and the idea that the fornzation of a projection is a causal step in the development of a cellular substructure. An argument is presented to show instead how it is plausible for substantial depvessiom to form in the pvesence of constitutional supercooling at dislocations threading the solid-liquid interjace. THE development of constitutional supercooling during growth from the melt leads to the formation of the cellular solidification substructure. This well-founded association between structure and instability has been basic in understanding cellular substructure and micro segregation; however, the initial formation of structure seems unclear. Rutter and Chalmers,&apos; in definitive experiments and theory, noted that in the presence of constitutional a planar interface might break down: "resulting in the formation of a small projection on an initially plane or uniformly curved interface." That is, the breakdown from a planar to a cellular interface was implied to be initiated via a projection into the unstable liquid. Later, Walton et (11. found that a structure of isolated projections, termed "pox", appeared at solid-liquid interfaces decanted under growth conditions near the onset of constitutional supercooling; the pox were taken as the indication of the instability promoted by the supercooling. Tiller and Rutter4 in their extensive work studied the shape transitions at decanted interfaces which were generally observed to proceed as— pox, "irregular cells", elongated cells, regular (hexagonal) cells, and so forth. The pox varied in size from lo-&apos; to 1CT4 cm, and tended to disappear as cells increased in number and regularity, but as noted,4 the first real array of cells did not seem to be a development from the pox. In fact these authors implied a lack of connection because they stated that the pox are denser on "irregular cells", and as cell boundaries increase in number (i.e., the cells become smaller) there is less need for the pox which do dis- appear. Thereafter, most authors dealing with either experiment or theory have accepted the reality of pox and have used them as a criterion for the onset of constitutional supercooling. In contrast, Spittle, Hunt, and smiths have now suggested that pox are irrelevant artifacts comprised of such things as entrapped oxide. This proposal invokes the observations of weinberg6 and chadwick7 each of whom have shown that the act of decanting leaves a residual liquid on a decanted interface; the remnant solid layer of the order 10 p may thus contain particles that might have been transported from the external surfaces, or elsewhere, during decanting. With the incentive of this suggestion,= some further experiments and a reexamination of the literature have been conducted, in order to question the validity of pox as evidence of an instability and to examine the initial development of the cellular substructure. 1) EXPERIMENTS Single crystals of zone-refined tin (-99.9999 pct) were grown from the melt in a controlled fashion with various, small concentration additions of lead and antimony, for which ko < 1 and > 1, respectively. The crystals were decanted at conditions near the onset of constitutional supercooling and were thus appropriate for observation of slight perturbations. It was possible to observe two types of small departure from smooth or "planar" interfaces in both cases of lead or antimony additions. Some were projections and others, if in regular array of any type, were depressions. The crystals were etched with suitable reagents progressively dissolving the decanted interface surface; projections left no record, but depressions were continuously associated with spotlike areas contrasting with the rest of the interface. Traverses were made with the beam of an electron microprobe across the regions of contrast; with lead addition the persistent spots were lead-rich, and with antimony addition the persistent spots were antimony-poor. This is consistent only with a dominant role for depressions, because if the projections had left spots but were incorrectly catalogued, a reversed observation should have been made; that is, the Pb(ko < 1) should have been depleted and the Sb(ko > 1) enriched. In the work of Cole and inegard, and elewhere, regular arrays of structure associated with the initial stage of instability have been shown, in photographs and represented as pox or projections. We believe this to be erroneous, by inference, since whenever a regular array was observed, in the present examination, it consisted of depressions, regardless of the nature of the solute, ko 1. Fig. 1 is reproduced8 as an ideal example of the possible optical illusion involved; the observer can satisfy himself from the distribution of illuminated areas that the markings are depressions. Fig. 2 from the present investigation is an interference photograph of an interface similar to that in Fig.

Jan 1, 1967

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950