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By Thomas Leonard Watson

SULPHIDE ore-bodies of more or less lenticular shape occurring in metamorphic crystalline schists, gneisses, and. slates, and conforming closely in strike and usually in dip to the inclosing rock, have been recognized and described along the, Atlantic seaboard from Quebec to Alabama. The ore-bodies do not entirely conform, in all cases, to the structure of the inclosing schists, but they sometimes cut across the foliation in dip, though conforming more closely with the direction of strike. In composition the principal sulphide mineral is usually pyrite or pyrrhotite; or both, accompanied by copper, frequently gold, and almost always some sphalerite and galenite. Other. metallic ores are, so far as these sulphide bodies have been investigated, less common; silver is not uncommon, and in some of the pyrrhotite masses nickel is present in quantity sufficient to be commercially valuable. Cobalt frequently accompanies .the nickel, usually in smaller amount, and the two vary much in relative proportion. Quartz and calcite are probably the most common of the, non-metallic minerals. A number of silicate minerals are frequent representatives in one place or another; garnet, amphibole, biotite, pyroxene, zoisite and others. The sulphide bodies of Virginia, comprising both pyrite and pyrrhotite, are among the most extensive along the Atlantic seaboard. Among the pyrite bodies may be mentioned the well-known and extensively worked mines of Louisa and Prince William, counties, located on' the main pyrite belt (A, Fig. 1) of the middle and northern, eastern Piedmont region in Virginia, and among the pyrrhotite bodies is the famous " Great Gossan Lead "(B, Fig. 1) of the Floyd-Carroll-Graysou coun-

Sep 1, 1907

By R. H. Adams, A. M. Khan

The Huntington Beach oil field is on the Pacific Coast, southeast of the City of Los Angeles (Fig. 1). It lies both onshore and offshore. Most of the onshore section is operated by Standard Oil Co. of California, WOI. The Tar reservoir is of upper Pliocene age, about 200 ft thick, and consists principally of fine-grained, unconsolidated, somewhat shaly sand, with thin inter-bedded shale stringers throughout (Fig. 2). The reservoir is a broad, highly faulted, elongated anticline, with an areal extent of about 370 acres. Most of the faults bisecting the structure are normal, trend north-south, and are the main cause of reservoir discontinuity (Figs. 3 and 4). From 1964 to Dec., 1967, 259 steam stimulations were performed on a total of 125 Tar sand wells. Eighty-six new wells were drilled and steam stimulated. Of the total, 96 have been stimulated twice, 34 three times and 3 four times. During this same period, a two-injector steam drive pilot has been in progress. The response obtained from this project has been compared with the response to cyclic stimulation. This paper presents an analysis of the field observations for the two methods of thermal recovery. History of Development Drilling to the Tar pool commenced in 1924 with an initial well production of 40 to 50 B/D of 12o API gravity oil. Complete primary development of the pool has been spread over several years. Approxi- mately 40 wells were drilled during the first phase of development, which was completed in 1945. The subsequent primary development started in 1960 with initial well productions of 30 to 40 B/D oil. Thirty-seven wells were completed in the Tar pool during this phase. For the most part, slotted, gravel flow packed liners have been used in the wells in this pool. A cyclic steam stimulation pilot was initiated in March, 1964. Based on the very successful stimulation in the pilot area, the cyclic stimulation project was expanded to include all of the Tar pool wells producing at the end of 1965 (Fig. 5). Also, a development drilling program was begun at this time. To date, 86 new wells have been drilled under this program. The number of wells drilled each year in this secondary phase of development is also shown in Fig. 5. New Well Completion Practices Most of the new wells have been completed to produce from both the Upper and Lower Tar zones. Generally, a casing stub is cemented from the top of Lower Tar to the base of clean Upper Tar sands to exclude intermediate water-bearing sands. The water string is then cemented from the top of Upper Tar to about 1,500 ft with neat cement and 30 percent silica flour. The annulus from 1,500 ft to surface is then filled with a petroleum-based gel through a high-temperature port collar. Once again, a history of sand-free production dictated the use of 60-mesh gravel flow packed liners. The Upper and Lower Tar

Jan 1, 1970

By W. L. Martin, J. N. Dew, H. B. Steves, M. L. Powers

This paper presents and discusses the results obtained during a pilot test in the Loco field in southern Okla homa. The test was conducted in a 2%-acre pattern that was part of a 20-acre conventional waterflood pilot area. The conventional flood was well past its economic limit when the hot waterflood was initiated to obtain technical information and operating experience. Temperature data from nine observation wells showed that about 75 percent of the pattern was affected by heat, and that heat losses were severe in the pilot pattern. About 60 percent of the injected heat was lost to overburden and underburden zones during hot-water injection. Wellbore heat losses were held at tolerable levels at the shallow depth of the test by providing a low-pressure air annulus between the injection tubing and well casing. Hot water provided water injectivity increases of 200 to 400 percent. The hot water channeled across the lower portion of the oil sand in three directions through zones of relatively high water saturation. There was no conclusive evidence that natural fractures or pressure partings aflected the flow of fluids in the pilot pattern; however response undoubtedly was aflected by localized pressure gradients and by injection-production rate ratios. The results showed that hot waterflooding increased oil recovery in a reservoir containing 600 cp oil. The total tertiary oil production from the pilot pattern area was 3,896 bbl or about 156 bbl/acre-ft swept by heat. The corre.sponding WOR was about 34:I. Description of the Hot Waterflood Process To hot waterflood an oil reservoir, water is injected that has been heated to a temperature substantially higher than the original reservoir temperature, but lower than the vaporization temperature of water at the prevailing pressures. In the reservoir the hot water flows continuously into cooler sand and rapidly loses heat to the sand until it has been cooled to the original reservoir temperature. Thus, a heated zone and a region or "bank" of cooled water begins to accumulate immediately after hot water injection is started. This bank of cooled water continues to grow ahead of the heated zone, which also grows, but at a slower rate. This occurs because heat transfer is almost instantaneous, and the ratio of heat capacities of water to rock is such that two or three unit PV of hot water must be injected to heat a given unit bulk volume of the reservoir. The primary displacement mechanism is the same for both hot and conventional cold waterfloods; i.e., "piston" displacement occurs at the original reservoir temperature. The incremental benefits of hot waterflooding usually occur long after the breakthrough of cold water at producing wells, and the increased oil recovery necessarily is accomplished with high WOR's (water-oil ratios). Heat decreases the viscosity and density of oil and water. These effects result in more rapid and increased recovery of secondary or tertiary oil. If the cost of the required heat is low enough, the ultimate oil recovery of a hot waterflood should be increased substantially over what would be expected at the economic limit of a conventional cold waterflood. The economic benefits of any hot-fluid injection project depend primarily upon the cost of the heat required to produce more oil at an increased rate. This cost depends in part upon the amount of heat lost to surrounding formations. Heat loss depends upon reservoir thickness, water injection rate and temperature, the depth of the formation, well spacing, and the characteristics of the reservoir rock and surrounding formations. In general, percentage heat losses decrease as injection rate and reservoir thickness increase. Although it is an old idea, hot-water injection has not received widespread field application in the oil industry as a drive process. Much of the original field work with hot water was done in Pennsylvania fields where water permeabilities and injection rates are low. In these cases, hot-water injection was used primarily as a means of increasing in-jectivities — not as a recovery process. Ramey' recently has published an excellent review of the development of hot fluid injection processes. Recent publications"' and our own experiences now indicate that hot water or steam injection also can effectively increase the oil recovery from reservoirs containing viscous crudes. However, the economics of these methods as displacement processes have not been established. Several theoretical predictive techniques have been published (for a review see Ramey'), but simplifying assumptions make

Jan 1, 1969

By Frank C. Roberts

Neglecting the hydrogen and hydrocarbons, 1 will assume the following analysis as a fair average composition, by weight, of the waste gases escaping from a coke-burning blast-furnace: CO2............17.25 CO,............25.25 N,.............57.50 100.00 The 25.25 CO requires for combustion 62.6 of air, or 11.398 of oxygen, necessitating the passage of 48.202 nitrogen into the products of combustion. The latter, therefore, have the following composition: CO2,,............ 56.9 N,............105.7 Tile total specific heats of these quantities of the respective gases are 12.31 and 25.79, giving for the combined product, 38.1 approximately. That is, the product of combustion will absorb 38.1

Jan 1, 1889

By Roswell H. Johnson

The principle of sliding or graduation in royalties is accomplished either by the block, period, cumulative, or class method. The block method calls for a very low royalty rate on all oil produced up to a certain amount. This amount would normally be that which is believed to suffice to repay the cost of the well. A higher rate would be charged after the well is making a profit. This method, common in many industries, is peculiarly inadaptable to any industry such as this where the productivity per day of the units gradually and inevitably decreases. This, for reasons given later, is because it forces an early abandonment of the well and so offends against conservation. In the period method, the royalty rate is changed by some definite amount when the well produces less than a specified quantity per day or other given unit of time. While simple to explain, it operates badly because a great deal is made to depend upon a small reduction in production, whereas the reduction as a matter of fact declines rather erratically owing to the exigency of lease management, connecting of tankage, and vagaries of the gaugers. These disadvantages are obviated by the cumulative method. In this method, all the production less than a certain amount per week has one rate of royalty, or none at all, and the oil produced in excess of that amount pays an additional rate of royalty. In the long run the calculation is probably no greater than with the period method, for simple tables will be published and printed in the oil papers that can be cut out, enabling quick readings to be made. Even without the table the calculation is easy with the few royalty rates, two or three, which would be used. In this method, the amount paid in royalty declines gradually, rather than suddenly as in the period method. The following reasons might be advanced for the adoption oi cumulative royalties: 1. To distribute the burden in accordance with the capacity to pay. This principle is a unique one in business, although familiar in taxation. This is because it does not distribute reward in proportion to efficiency.

Jan 1, 1916

By Ernest R. Darby

If the correct balance between fuel and air is maintained in an open-flame furnace,' little chemical action may be expected between the products of combustion and the metal being melted. Physical' changes in the metal are the object of the melting operation, and indirectly, under certain conditions, may be the cause of subsequent chemical actions. If sufficient heat has been introduced into the metal to bring about the change from the solid phase to the liquid phase, and still further from the liquid to the vapor phase, the metal vapor in all probability will be carried from the furnace by the exhaust and rapidly combined with the oxygen of the outside air. The charge being melted in the furnace may contain elements which are chemically inactive at normal temperatures but which will form compounds at the elevated temperatures of the metal bath, or even at a lower degree. Such indirect chemical actions are very confusing and often lead to incorrect conclusions regarding furnace atmospheres. In the open-flame furnaces used in the melting of bronze, the furnace atmosphere is spoken of as being either neutral, oxidizing or reducing in its effect upon the metal. A neutral atmosphere, as mentioned, is generally considered as the atmosphere of the furnace that will produce melted bronze, neither oxidized nor gassed. It is in effect an atmosphere which is not directly the cause of any chemical action. In such an atmosphere absolutely pure metals may be melted and poured without the absorption of gases or the formation of metallic oxide. The metal has undergone a simple, physical change. An oxidizing atmosphere is one in which the air introduced to the furnace is in excess of that required to complete combustion of the fuel used. The oxygen of the excess air may combine with the metal being melted to form metallic oxide, which may or may not be dissolved by the metal. If an absolutely pure metal is melted in a furnace operating with such an atmosphere, a portion of the metal charged may be converted into metallic oxide, the amount depending upon the duration of the

Jan 1, 1930

By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By Frederick J. Pope

The protaxis of the North American continent consists, as is well known, of a large V-shaped area of Archæan rocks, which lie for the most part in the Dominion of Canada, and occupy an area of not less than 2,031,000 square miles. The western limit of this area extends from 'Lake Superior in a northwesterly direction to the Arctic Ocean, the southern is found along the Lower St. Lawrence as far as Labrador. A minor area, spoken of as the Adirondack region of northern New York, has a somewhat broken connection with the main body in a narrow band of igneous rock, which crosses the Upper St. Lawrence where it leaves Lake Ontario. The ancient crystallines are also presumably beneath all the later sediments, hut the above brief description outlines their principal exposures. This great rock-complex consists, for the most part, of a series of gneisses, which present great variations in both structure and composition. In certain sections areas of gneisses of the general composition of granite, and remarkably uniform in character, prevail. They consist largely, if not exclusively, of crystalline rocks in which a banding or foliation has been induced by pressure. These rocks constitute the basal member of the Laurentian system, and by later writers have been referred to as the Ottawa gneiss. In other and quite extended areas, gneisses, regarded by many as composed of altered sediments, are associated with crystalline limestones, quartzites, and much injected igneous matter. To this series the term Grenville has been applied. Both of these series of gneisses are penetrated by various igneous masses, of which the most important are great intrusioiis of several members of the gabbro family, such as anortho-sites, norites, pyroxenites, and gabbros proper; the whole form-

Jan 1, 1900

By J. D. Vincent, Paul A. Weyler

Climax Molybdenum's plan for the Henderson 30,000 tpd molybdenite plant didn't just happen. It slowly evolved over a period of 3% years. Many plants cannot afford similar delays, but the Henderson project will take about 10 years to complete from the time the orebody was first discovered until production begins. Pilot plant testing results with both the single stage and two-stage semi-autogenous grinding circuits were highly favorable in terms of operating costs reduction-so much so, that the Amax subsidiary made the decision to go with semi-autogenous grinding for the Henderson mill.

Jan 5, 1972

By F. C. Noyes

DAME Nature was in a generous mood when she distributed widely over the face of the globe numerous deposits of phosphate rock from which man can make phosphatic festiIizer to replace the phosphate re- moved from the soil by crops. The principal deposits are readily accessible to the world's greatest consuming areas and most of them are such that mining operations can be carried on at relatively low cost. The world's known reserves shown in Table 1 are sufficient to last well over 2000 gears at the present rate of consumption. Before giving a brief outline of the phosphate rock industry of foreign countries let us try to get a picture of the movement of phosphate rock throughout the world in 1938, the last full normal calendar year where it came from and where it was consumed. Table 2 shows the origin and finial destination of world shipments in 1938 by grand divisions. Table 3 (p. 499) shows shipment9 of phosphte rock to each country in Europe. Europe is seen to be by far the world's greatest market and the French North African mines the world's most important producers outside of the U. S. A.

Jan 1, 1944

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period April 1 to 15. William B. McKinley, New York, N. Y Collier Cobb, Chapel Hill, N. C. C. W. Goodale, Butte, Mont. E. P. Fleming, Guayacan, Chile. D. C. Brown, San Luis Potosi, Mex. Albert Sauveur, Cambridge, Mass. W. H. Rettie, Yonkers, N. Y. H. M. La Follette, La Follette, Tenn. Mark B. Kerr, San Francisco, Cal. E. Fleming L'Engle, New York, N. Y. H. W. Turner, San Francisco, Cal. H. Garlichs, St. Louis, Mo. Frank M. Leland, Mackay, Idaho. Henry Hay, London, England. Sir Robert Hadfield, London, Eng. Edward J. Way announces that his agreement as consulting engineer in South Africa for the Anglo-French Exploration Co., Ltd., having terminated, he will engage in professional consulting work with headquarters at 135 Cullinan Buildings, Simmonds St., Johannesburg, South Africa.

Jan 5, 1914

By A. Perry Thompson

I- GeneRal Distribution, AppeaRance, and Relations ........ 563 11. Data fRom MicRoscopic Examination............... 568 1. Criteria for Distinguishing Primary from Secondary Minerals...... 568 2. The Leonard Vein Filling..................... 574 Quartz............................ 575 Pyrite............................ 575 Enargite............................ 576 Covellite............................ 578 Bornite............................ 581 Chalcocite........................... 583 Chalcopyrite.......................... 586 3. The Fault-Vein Covellite..................... 587 The Speculator Ore........................ 587 The East Gray Rock Ore.....,.............. 589 4. Other Occurrences of Covellite.................. 591 111. Conclusions........................... 592 1. The Replacement of Minerals..................592 2. The Character of Mineralizing Solutions .............. 594 I. General Distribution, Appearance, and Relations Mining in Butte has seldom encountered covellite in commercial quantities. The notable occurrences, extending vertically and laterally perhaps several hundred feet, presented scattered, bladed lenses of this mineral in a matrix of quartz, pyrite, enargite, bornite, and chalcocite. But under the microscope covellite is seen to be widespread in the Butte ores, though in such small quantity that megascopic examination will not discover it. In early mining operations covellite was found in the Gray Rock vein, a member of the Blue vein system. As described by Sales,' it persisted as an occasional ore mineral, associated with quartz, pyrite, tetrahedrite, bornite, chalcocite, and minor amounts of sphalerite, from the 700-ft. to the 1,200-ft. level of the East Gray Rock and Diamond mines. Crushed quartz-monzonite and later quartz completed the vein filling between

Jan 1, 1916

By G.A. Moore, C. E. Sims

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By C. E. Sims, G. A. Moore

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By David Segura

THE Huitzuco mercury deposits have been described by C. W. Vaupell,1 therefore the general information such as location, history, production, etc. will not be repeated here. The present owners acquired the property when the deep levels of the Cruz mine were flooded, and it was believed that a relatively large tonnage of low-grade ore and fills would be encountered in the flooded section, because f the early mining methods used in the Cruz mine. The mine was partly unwatered and about 187,000 tons of fills was pit-sampled in the San Cayetano stope. These fills average 2.4 kg. Hg per. ton. During the period of maximum production at Huitzuco, the ores were sorted in the mine and cobbed into 3-in. pieces, which were treated in Scott furnaces. Large pieces of raw ore are found in the sinter, and it is indicated that both recovery and, costs were not very satisfactory. Recent practice has been to treat the ores in closed retorts made of 10-in. pipes. Because f the presence of combined antimony in the mineral livingstonite (HgS.2Sb2S3) and considerable native sulphur, little or no metallic mercury is recovered in the condensers and a second retorting of the condenser muds is-necessary. This makes the treatment of the ores expensive and tends to low recoveries of mercury. The prin-cipal costs of retorting are, in their relative order: (1) fuel, (2) low recov-ery of mercury, (3) replacement of retort pipes, (4) labor.

Jan 1, 1938

THE first session of this meeting was held Tuesday evening, in the chamber of the Common Council, the President, Mr. David Thomas, in the chair. Mayor Carroll, of Troy, gave a cordial welcome to the Institute, which was responded to, on behalf of the Institute, by the first Vice-President, Mr. R. W. Raymond. The Council reported the names proposed for membership with recommendation for election. The following named gentlemen were duly elected: Anthony, J., . .Williamstown, Pa. Babcock, George, . . .Troy, N. Y. Blake, Theo. A., . . . . . . Sa n Francisco, Cal. Blossom, T. M., . . . . . . New Pork. Boalt, James A., . . .San Francisco, Cal. Bowman, Amos, . . . . San Francisco, Cal. Chester, Prof. A. H., . .Clinton, N. Y. Dewey, C., . Pittsfield, Mass. Dock, Gilliard, . Shamokin, Pa. Emerson, O. D., . .New York. Endres, John J., . .Pittsburgh, Pa. Firmstone, Frank, . Easton, Pa. Fowle, W. B., . Philadelphia, Pa. Frazier, Prof. B. W., . . .Bethlehem, Pa. Gardner, George A., . New Pork. Goodyear, Watson A., . .6an Francisco, C al. Griswold, Chester, . Troy, N. P. Griswold, J. A.,* . . .Troy, N. Y. Hague, J. D., . . .San Francisco, Cal. Hahn, 0. H., . .Eureka, Nev. Harkness, T. C., . . . . . . Wilkes-Barre, Pa Harris, Samuel, . . .Hudson, N . Y. Henry, &. T., . Oxford, N. J. Holley, A. L., . .Brooklyn, N. Y. Howe, H. W., . . .Troy, N. Y. Hunt, Dr. T. Sterry, . Boston, Mass. Jannet, J., . Troy, N. Y. Knapp, John A., . .New Pork. Laughlin, Henry A., . . .Pittsburgh, Pa.

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By S. F. Shaw

The Sierra Mojada mining district is situated in western Coahuila, about 8 km. east of the Chihuahua state line, and about one-half way from the northern to the southern extremity of the state. It is at the terminus of the Mexican Northern R. R., 125 km. northeast of Escal6n, Chihuahua; also about, 240 km. due west of Monclova, Coahuila. The altitude is approximately 1500 m. above sea level. The Sierra Mojada valley is about 10 km. long, from east to west, with a width of 1 to 2 km. It is approached from the east through the Puerto del Oro, where the Mexican Northern R. R. enters the valley; the slope from west to east is gentle. The Sierra Mojada, of which about 300 m. is an almost vertical wall, bounds the valley on the south side; on the north side, the slope to the crest of Sierra Planchada is more gradual, rising only 200 or 300 m. above the valley. Water is relatively scarce in the district, and there are no running streams. The rainy season, usually beginning at the middle of June, lasts through July, and occasionally into August or September. In some years the rains fail entirely. The slope of the ground is such that nearly all the water immediately runs off. The arroyos along the flanks of the mountains are not very deep, but in heavy rains, sometimes approaching cloudbursts, a tremendous volume of water rushes down them, carrying large boulders. A certain amount of seepage collects in the agglomerate, lying below the conglomerate, and is retained in the local fractures. Some shallow wells have been sunk in this agglomerate, and one well over 150 m. deep was sunk on the Volcan ranch, supplying about 76 1. (20 gal.) per min. A considerable supply of water is collected in large earth reservoirs in and below the town of Esmeralda. In ordinary years this supply will last until January or February, after which the Volcan well has to be depended on until the next rainy season. Vegetation is scarce, aside from scanty scrub oak and other brush in the mountains, and a few mezquite, locust, pepper, and cottonwood trees

Jan 1, 1923

By S. F. Shaw

The Sierra Mojada mining district is situated in western Coahuila, about 8 km. east of the Chihuahua state line, and about one-half way from the northern to the southern extremity of the state. It is at the terminus of the Mexican Northern R. R., 125 km. northeast of Escal6n, Chihuahua; also about, 240 km. due west of Monclova, Coahuila. The altitude is approximately 1500 m. above sea level. The Sierra Mojada valley is about 10 km. long, from east to west, with a width of 1 to 2 km. It is approached from the east through the Puerto del Oro, where the Mexican Northern R. R. enters the valley; the slope from west to east is gentle. The Sierra Mojada, of which about 300 m. is an almost vertical wall, bounds the valley on the south side; on the north side, the slope to the crest of Sierra Planchada is more gradual, rising only 200 or 300 m. above the valley. Water is relatively scarce in the district, and there are no running streams. The rainy season, usually beginning at the middle of June, lasts through July, and occasionally into August or September. In some years the rains fail entirely. The slope of the ground is such that nearly all the water immediately runs off. The arroyos along the flanks of the mountains are not very deep, but in heavy rains, sometimes approaching cloudbursts, a tremendous volume of water rushes down them, carrying large boulders. A certain amount of seepage collects in the agglomerate, lying below the conglomerate, and is retained in the local fractures. Some shallow wells have been sunk in this agglomerate, and one well over 150 m. deep was sunk on the Volcan ranch, supplying about 76 1. (20 gal.) per min. A considerable supply of water is collected in large earth reservoirs in and below the town of Esmeralda. In ordinary years this supply will last until January or February, after which the Volcan well has to be depended on until the next rainy season. Vegetation is scarce, aside from scanty scrub oak and other brush in the mountains, and a few mezquite, locust, pepper, and cottonwood trees

Jan 1, 1923

A. A. CENTER*—This paper reminds me of the beginning of the work of the Electrolytic Zinc Company of Australasia. Early work for this Company, as some of you may know, was done at the Bully Hill Plant in California. After working there for some time Herbert Gepp, now Sir Herbert, came to the Anaconda Co. plants in Montana where I met him. He spent some months there, in fact almost a year if I remember rightly. That was when we were breaking in the new electrolytic zinc plant at Great Falls, Montana. From there he went back to Australia and started in on the plant there. I believe they had an original plant of about 20 tons per day of cathode zinc. We heard from them for some time, until they were able to go along on their own, and they have done very well ever since as you have heard. Their practice, (the flow sheet, the leaching practice), has been quite different as reported in the paper and apparently they are still following that practice to some extent. While the earliest work on selective flotation was done down in Australia, the big companies there, strange to say, were far behind the American companies in taking it up; and it is only in comparatively recent years they have gone to the alkaline circuit and dropped out thereby more of their iron and lead. The zinc plant now is up to a capacity of 100,000 tons a year and I believe that may be notched up to about 105,000. T. H. WELDON*—I would like to ask

Jan 1, 1950