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By Archer Wheeler

The Boston & Montana Reduction Works at Great Falls, Mont., was formerly the reduction works of the Boston & Montana Consolidated Copper & Silver Mining Co., and continued as the reduction plant for the independent company until .June 1., 1910, when the consolidation of a large number of the operating companies of Butte was effected. It then became merged in the Anaconda Copper Mining Co. as the Boston Montana Reduction Department of the Anaconda Copper Mining Co. The history of copper converting at this plant, while not covering the entire period of the commercial use of the process in this country, does cover by far the larger part of it, and as the operations and appliances of the process have undergone many changes during the time, it may, perhaps, be of some interest to put the record of these changes into permanent form. The plan followed in the preparation of this paper has been to give first a brief chronological record of the principal events and changes and then, even at the risk of some repetitions, to give more detailed account, of some of these changes under separate headings. The headings for the complete paper are as follows: 1. General Chronological Review. 10. Development of Different Classes 2. Mechanical Manipulation of Converters After Class I. 3. Casting of Finished Copper. 11. Basic Lining. 4. Tamping of Linings. 12. Number and Size of Tuyeres. 5. Early Acid Linings. 13. Cast Copper Tuyeres. 6. Acid Linings With the Use of Ore. 14. Efficiency of Air. 7. Introduction of Flux Through the 15. Size of Converter Mouth. Tuyeres 16. Height of Converter. 8. Bottom Blast. 17. Summary. 9. Disposal of Converter Slag.

Jan 8, 1913

By Oliver Smalley

EXCEPT for the work of Guillet, who conducted a systematic investigation on the zinc-replacing value of nickel in brass, and extended his investigation with a view to developing commercial high zinc content nickel brasses, the author does not know of any systematic research on the subject. The most promising commercial alloys and their physical properties obtained by Guillet are given below: Maximum Elonga- Reduction Copper Zinc Nickel Stress, tion, of Area, Brinell Tons Per Per Cent. Per Cent. Sq. In. 55.0 41.0 5.0 24.4 46.5 94 Sand cast. 22.6 27.0 90 Chill cast. 56.7 39.74 3.35 30.0 43.0 51.7 97 Casting annealed 2 hr. at 750° C. 33.9 33.0 50.7 144 Cold-drawn bar. 55.15 42.3 2.24 29.8 33.0 116 Casting annealed 2 hr. at 750° C. 32.3 29.0 151 Cold-drawn bar. These test results scarcely justify the use of such quantities of so expensive a metal, and could have been obtained from ordinary commercial brass. For purposes of comparison, the physical properties of ordinary brasses, ranging from 70 per cent. to 50.1 per cent. Cu in both the cast and normalized1 conditions are included in Table 1. These incidentally furnish a useful standard of the properties of castings and of rolled, extruded and forged brass when correctly annealed. A close study of some of the well-known special brasses containing nickel reveals a series of alloys which bewilder by their complexity, and one can only hazard a guess at the function and commercial value of each of the many elements used.

Jan 10, 1925

By R. W. Raymond

There is apparently no end to the doubts, inconsistencies and absurdities in which the courts of our mining States and Territories are involved in their attempts to apply to conditions of ever-increasing complexity the provisions of our anomalous mining law. In previous papers, I have called this statute " the law of the apex," because it based upon that vague, novel and mysterious condition the most important grant of title. But the apex is scarcely a more essential feature than the end-lines and the side-lines; for the rights which it may confer may be limited in various ways by these; so that we have, in many a case, the most ridiculous result that the United States, in return for the money of a citizen, conveys to him with much solemnity, under its broad seal, nobody knows what, bounded nobody can tell how. A decision recently made at Butte by Judge De Wolfe, of the United States District Court of Montana, in the case of King et al. vs. The Amy and Silversmith Mining Company, furnishes a fresh illustration of this criticism. The diagram on the following page, constructed without precise regard to courses and distances, simply to assist in the statement of the essential features of the case, will, 1 hope, make clear the principles . involved : The plaintiff occupies a location (the Nonconsolidated) adjoining on the north the defendant's location, a b c d (the Amy), and the disputed mining-ground lies, let us say, in depth under the point W, that is, on the dip of the vein, VD, but not under the surfacelocation, a b c d. The defendant has the prior title, and claims this ground under its extra-lateral right. It is admitted that the apex does not cross the end-line, a d, and does cross the side-line, a b. Whether it crosses, at the other end of the location, the end-line, b c

Jan 1, 1889

Discussion of the paper of Willis T. Burns, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 2011 to 2049. PROF. JOSEPH W. RICHARDS, South Bethlehem, Pa.:-I think Mr. Burns spoke of two unusual conditions which he has at his plant, namely, that he uses directly converter anodes and very high current density. He did not mention another condition : the very low cost of power, which circumstance, I believe, is responsible for some of the peculiarities of his plant noticed by us from the East. I am struck by the rather low ampere efficiency which Mr. Burns obtains, and in looking over the plant thought that there was a considerable leakage from one tank to the other, and that the ampere efficiency could be increased by looking after the leakage of electricity front one tank to the other.

Jan 11, 1913

By G. Derge, Ling Yang, John Henderson

Self-diffusion coefficients of aluminum have been measured by the capillary reservoir technique in liquids of the CaO-SiO2-Al2O3 system containirg equimolar portions of CaO and SiO2, in the temperature range 1400o to 1520oC. For the melt containing 6.0 mole pct Al2O3 the results can be expressed by the equation D = [(4.3 * 0.3) x 104] exp [(-85,000 * 17,500)/RT]cm~sec-'; for the melt containing 12.5 mole pct Al2O3, by the equation D = (5.4 i 0.2) exp [(-60,000 * 10,00O)/RT] cm2sec-: A concept of the constitution of these melts has been developed which proposes that the ratios O/(Si +Al) and Al2 O3/CaO determine the dominant species present. In recent years considerable work has been done on the system CaO-SiO2-A12O3 with a view to elucidating the structure of liquids of this system. Conductivity,' electromotive force, 3 density,4 and activity5 measurements have all contributed to an understanding of the problem, but as yet there is no entirely satisfactory theory that can account for all the observed experimental results. In principle, measurements of self-diffusion coefficients should give further information which is not obtainable in other ways. Self-diffusion coefficients for calcium, silicon,6 and oxygen7 have been measured. The present investigation extends the series of self-diffusion coefficient measurements to include aluminum and develops a concept of constitution for liquids of this system which is compatible with all the observed experimental results. EXPERIMENTAL The technique used in the measurement of the self-diffusion coefficient of aluminum was the capillary-reservoir method,8 A126 being incorporated in the melt contained in the capillary and inactive aluminum in the reservoir melt. This method was chosen because it minimizes convection currents' in the diffusion zone. It has the further advantage that the boundary conditions are such that a slight modifica- tion of Anderson and saddington's8 solution of Fick's Law yields an equation which requires measurements only of the length and the initial and final average specific activities of the solidified melt within the capillary. where t is the diffusion time, Co is the average specific activity of the melt contained in the capillary at t = O, C is the average specific activity of the melt contained in the capillary at t = t, 1is the length of the capillary, and D is the self-diffusion coefficient. The equation is of somewhat different form than those previously applied to high temperature diffusion studies because the specific activity of the melt in the reservoir was negligible both before and after diffusion. The diffusion apparatus is shown schematically in Fig. 1. It consisted of a silicon carbide resistance furnace containing the inactive melt in a graphite crucible, internal dimensions 7/8 by 4 in., enclosed in a 1 1/4- by 1 1/2- by 30-in. McDanel tube. A 3/8-in. McDanel thermocouple sheath to which graphite radiation shields and a graphite protection tube were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube the capillaries could be lowered into or raised out of the melt. Temperature was measured with a Pt-Pt 13 pct Rh thermocouple which was calibrated periodically against a standard couple. The furnace temperature was controlled to ± 5°C through the thermocouple immersed in the melt. Temperature variation over the depth of the melt was less than ± 3°C. The inactive melts were prepared from pure native quartz, assaying better than 99.9 pct SiO2, A.R. grade A12O3 and A.R. grade CaCO,. The same quartz and CaCO3 were used in preparing the active melts, the

Jan 1, 1962

R. W. Balluffi (Atomic Energy Div., Sylvania Electric Products Inc., Bayside, N. Y.)—Since porosity is known to form in the copper side of Cu-Ni couples during diffusion24,25 it is of importance to consider this factor in interpreting the large variations of chemical diffusivity with copper concentration reported for this system. The presence of porosity may affect the measurement of D in two ways: 1—density changes in the couple invalidate the usual solutions of the diffusion equation, and 2—the pores may act as short-circuiting paths when transport through the vapor or along internal surfaces is appreciable or else as open circuits when these effects are small. The error produced by the first effect may be estimated by a graphical analysis. Fig. 8 shows the porosity generated in the copper side of the Kirkendall interface of a pure nickel vs pure copper couple after diffusion for 350 hr at 1040°C in hydrogen. In Fig. 9 the actual diffusion curve which would be obtained by the usual slicing technique is shown as a solid line drawn to the same scale (from the data of da Silva and Mehl"). The amounts of porosity (obtained by lineal analysis) and of nickel are graphically represented by the hatched areas. The standard solutions of the diffusion equation are valid only when all volume elements of unit length and unit cross section contain equal numbers of atoms." It is possible to correct the experimental curve to satisfy this condition by shrinking the couple in the direction of diffusion in such a way as to eliminate the porosity.* The corrected diffusion curve obtained after

Jan 1, 1954

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

Last year the authors presented a paper that discussed the various electrical measurements they perform in drill holes, which they name "electrical coring."' The object of the present paper is to give a brief account of the points of scientific interest that have been elucidated by further field work and laboratory research, as well as the economic results that have been attained recently. The practical examples given in this paper are drawn, for the most part, from the field work performed in Russian oil fields during the years 1931 and 1932. This is due to the fact that, thanks to the comprehensive cooperation of the Russian geologists and scientists, the authors are allowed to make public a large amount of recant information. In other countries in which the authors are engaged in similar work, the competition between private companies makes it imperative, for a considerable lapse of time, to avoid publication of the results obtained. The following points will be discussed successively, under separate headings: 1. Electrochemical phenomena in drill holes. 2. Stratigraphic correlations and tectonic studies. 3. Relations' between the productivity of oil horizons and their electrical resistivity. 4. Location of coal seams. 5. Summary and conclusions. Electrochemical Phenomena in Drill Holes Technical Publication 462l described the author's discovery concerning the existence of important differences of potential spontaneously gener-

Jan 1, 1934

By Maurice Grieves

The great majority of shafts constructed today are still excavated by drilling and blasting, a method which changed very little in over 100 years until the introduction of the mechanical lashing unit and cactus grab by the South Africans, which enabled muck to be removed as fast as massive hoisting systems could handle it and resulted in very rapid rates of sinking. Record breaking month's performances were achieved at -Hartebeestfontein No. 4 shaft, October 1960-337.1 m; Western Reefs No. 4 shaft, October 1961-340.7 m; and Buffelsfontein eastern twin shaft, March 1962-381.2m. The method was very labor-intensive, requiring a crew of over 60 workers at the shaft bottom during the drill cycle. Safety precautions were strict, but in the drive to achieve rapid advance, cases of personal injury were still somewhat high because of the large number of people engaged in this potentially hostile environment. The South African method, as it came to be referred to throughout the rest of the world, was adopted in the United Kingdom in the late 1950s in a modified form with greatly reduced manpower and nonsimultaneous sinking and lining, which was insisted on by the British Mines Inspectorate. In that instance, it was successfully used to sink the 7.3-m-diam concrete-lined shafts at Kellingley to 770 m depth, with rates of advance of over 90 m/month achieved, a British record at that time. During the sinking of the 1.15-km-deep twin shafts at Boulby potash mine in the UK in 1970, the method was again used, but for the first time ever in Britain exemptions from the mining code permitted the use of crash beams, crash doors, jack catches, and semi-simultaneous sinking and lining techniques. New British shaft sinking records of over 120 m/month were achieved in both shafts. Similar equipment and techniques were used in the early 1970s to sink several deep shafts in Canada, notably Creighton #7 and the Con zinc mine at Yellowknife in the NW Territories. Today, this equipment is standard for deep shafts in the US and the rest of the world. However, with the tremendous escalation in mining labor costs, the impact of health and safety legislation, and environmental regulations, coupled with a very real shortage of miners willing to work in this exposed situation it was apparent that an alternative to the labor-intensive conventional method of shaft construction had to be found. Recognizing the trend is inevitable, one or two major German shaft sinking contracting firms began to take a fresh look at full face boring techniques applied to tunnels and raise bored shafts. The results were most encouraging. Tunnel drivage techniques using moles had developed considerably from Colonel Beaumont's original channel tunnel machine circa 1880 to the superbly engineered Priestley machine selected to cut the British side in 1975 and the double shielded Robbins Grandori borer on the French side of the English Channel. Full face tunnel machines were being successfully used to drive uphill in inclined shafts in Austria and Switzerland. At Mapprag in Switzerland, the Demag mole drove the first (intentional) vertical transition and curve, and then went on to successfully complete the 730-m-long penstock shaft at an inclination of 35°. In Austria, the Wirth mole drove the Kaprun Glacier ski-lift railcar tunnel at record breaking rates of 457 m/MONTH (best 30 m/d) through green schist at an inclination of 29° for a distance of 3.35 km while the Hydro tunnel at Sarrelli in Switzerland was being driven by the Robbin's mole at an inclination of 35°. Simultaneously, extremely promising results were obtained using large assemblies of cutter discs on raise borer heads, such as the 4.87-m-diam X 460-m-deep shaft raised by Teton for Jim Walter Resources Inc. Bearing in mind that most mine shafts in the future (unless in exceptionally competent rock) will require some form of lining, and the trend will be toward deeper shafts as the more easily accessible mineral deposits become exhausted, it was seen that normal raise boring had definite limitations in vertical accuracy, in the limitation imposed by the drill string on the available torque that could be applied to the cutter head, and in the risk of collapse of the unsupported shaft rock wall in friable or jointed and fissured ground, since it is not possible to apply any form of temporary support until the permanent lining is being installed. A further problem was the economics of installing a subsequent lining, necessitating setting up a headgear and hoisting arrangement approaching in size that required for conventional drill and blast sinking and lining. Because of the economics, German contractors opted for a phased transition from drill and blast to the full face, rodless, out of the solid shaft mole, by starting off with a down-the-hole shaft boring machine -without a drillstring-but using a pilot hole to get rid of the muck.

Jan 1, 1982

By J. H. Klepinger, C. W. Goodale

I. Introduction....................567 II. Character oF the OrE................568 III. Old FluE System..................572 IV. Tests on Old FLUE System..............575 1. Aspiration Tests................. 575 2. Tests with Steel Settling Chamber........... 575 3. Test with Experimental Brick Flue........... 583 4. Testa on Blast Furnace Geses............. 591 V. Design of New FluE System.............. 597 VI. Main Dust Chamber................. 605 VII. Some DetailS of Construction ............. 609 VIII. THE Chimney.................... 616 IX. Operation of New FluE System............. 624 X. Temperatures and DraFTS............... 630 XI. Velocities and Volumes................ 632 XII. TeStS on the New FluE System............. 637 XIII. Conclusion..................... 643 I. Introduction. In the summer of 1909 the Boston & Montana reduction department of the Anaconda Copper Mining Co. completed a new flue system, at a cost of about $1,100,000, and as this includes the largest and highest chimney in the world, and some new features of flue construction, a description will be of interest. At the Spokane meeting of the Institute in September, 1909, a brief mention was made of this flue system, in discussing Mr. Brunton's presidential paper on the Progress of Metallurgy in the West, and a promise was given that when a long enough time had elapsed, so that operating results could be given, a paper would be offered. The smelting plant includes blast furnaces, MacDougall roasters, gas-fired reverberatories, and converters.

Jan 1, 1914

By O. Chanute

all of' level atid grade curve excepting Nos. 897, 898, 899, and 900, because of the impossibility of grouping them in the same nlonner, no two Iraving the chemical composition and physical prnprtiw as tho only v:iriubles. Phosphorus ~tnits have been taken to show the relatia h:wdnes. Of these 16 groups, 10 decidedly indicate slower wear firr tile harder rail. Of the remaining 6 groups, three (groups 2, 9, and 15) come well within the limits of error (.25 pound per yard) inherent in the palculation of the data as pointed out by Dr. Dndley; they catrnot, therefore, be considered tls exceptions. Group 2 and 15 arc but little outside of the limita of error. Rail 923 of group 9 is obviously abnornlal. This is probahly due to its being overheated, which the chemical analysis shows might easily be the case, and which the physical tc~ts and its low specific gravity tend to c-nfirm. We inry say, then, thnt 13 of these 16 groups fairly indicate, if they do not definitely point out, th:kt, under the same condition% tbe harder rail gives the slower wear. Of course, these comparisons are too few to enable us to arrive at positive ~?o-nclusions; but indications thus obtained are, I believe, fir more vsluitblc and tresttvc~rthy than those fhzt averages rvottld give us, mnde up from any ~lumhr of rails under intloy difi~rcal, conditions. Finally, it, seems to me, that the conclusions arrived at earlier in my remarks, together with, and confirmed by the last, show strong evidence that, under the same conditions, the harder rail will givc the slower wear. 0. C~~anute, New York CITY: We are very much shlipl, 1 ant sure, to Mr. Sandberg for his paper upn " Rail Ryaifications and Rail Inspertion in Europe." We have in thp United States bithhrto Been inspecting mils sonlewl~at haphazard, and we ore glad to gtbt tfie results of Mr. Sandberg's long experience. We recognize that he was an)ong the first, if not the very firwt, to iipply mare rittional and scientific rules to the designing of irou rails., niora recently, to adapt tlitve rules to the clesigtting of steel I':I~]R, to conform to the oapaljilities and rqniretnento of this new n1:ttcrial. Although we have generally adopted, in this country, sectinns for hteel rails which marly of our railway men think even bottar than those of Mr. Snlldlmrg, he is neverthelees the Ieat3er in foot.iito11~ we have followed ever since it has been est~blished

Jan 1, 1881

By T. G. Decker, A. F. Witt, A. M. Gaudin

The historical development of the concept of contact angle hysteresis is reviewed. The measurements of contact angles reported in literature have all been made under static conditions. For the measurement of dynamic advancing and receding contact angles, four methods are described together with an evaluation of their precision. Three of these methods were adapted from devices already used for the measurement of static contact angles. The fourth method uses a new principle and apparatus and is the most accurate. While the relationship between surface tensions and the contact angle was extablished as early as 1805 by T. Young,' it was only in 1890 that the existence of contact angle hysteresis was reported by Lord Rayleigh. His observations, however, remained almost unnoticed. With the invention of froth flotation, the contact angle and its behavior became the subject of investigation. In 1907, L. Sulman and collaborators investigated the cause of discrepancies between recorded values of contact angles. They found that certain variations existed in most cases, but that definite maximum and minimum values of contact angles are obtainable. The difference between the maximum and the minimum contact angle in a given system was termed "hysteresis" by Sulman. First attempts to explain hysteresis were made by E. Edser. In the following years extensive studies of contact angles in various three-phase systems

Jan 1, 1963

By Zay Jeffries

Each generation accepts the developments of the preceding generations without full appreciation of the difficulties that had to be overcome or of the effect of any given development on society. Today, the production of pig iron is the yardstick with which general industrial health and progress are measured. So natural and logical does this seem to us, that it is difficult to picture conditions prior to the fourteenth century when pig iron was unknown. Not only was pig iron unknown but iron or steel could not be melted and poured into castings; all iron and steel articles were forged from sponge iron. All castings, as well as many worked articles, were made of non-ferrous metals or alloys. In many parts of the world, over long periods of time, not only was the annual exchange value of non-ferrous metals greater than that of iron and steel, but their combined tonnage was greater. At present, the value of the pig iron produced in a year is of the same order of magnitude as that of all non-ferrous metals combined; the tonnage of pig iron is, however, about twenty times that of all non-ferrous metals combined. Owing to lack of records, we will probably never know the relative importance of the various metals at all periods in historic times. A certain conclusion is that the iron and steel industry, since the discovery of pig iron and the cheap methods of converting it into steel, has grown at a much more rapid rate than the non-ferrous metal industries. Notwithstanding their fundamental fitness for man's needs, iron and steel owe their importance in no small degree to the low cost of production. The low cost was a result of increased knowledge of the production appliances and of the metallurgical processes. This increased knowledge is the key to our modern industrial civilization. It will remain for future generations to determine whether there is now going on a gradual change toward greater importance of the non-ferrous metals, as compared to iron and steel. The world's pig iron production in 1920 was slightly more than twice what it was in 1890, whereas the non-ferrous metals production in 1920 was about two and one-half times that in 1890. Every non-ferrous metal industry has shown marked growth during the last thirty years. During this period, the production of cop-

Jan 1, 1924

By Harold S. Morgan

INTRODUCTION The Waste Isolation Pilot Plant (WIPP) is being developed in southeastern New Mexico by the United States Department of Energy as a research and development (R&D) facility to demonstrate the safe disposal in salt of radioactive wastes resulting from defense activities. As part of the WIPP R&D program, a series of in situ tests will be performed to determine the behavior of drifts and storage rooms in the creeping salt medium (Matalucci, et al. 1982). Data obtained in these tests will be used to evaluate and improve numerical models used to compute the structural response of these drifts and rooms. Stress has been proposed as one of the parameters to be measured in the tests, and borehole inclusion stressmeters have been included in the instrumentation package. Cages of this type provide an indirect measurement of stress change in that they actually monitor borehole displacements which are then related to changes in the in situ stress away from the borehole. The relationship between stress and displacement is highly dependent upon the constitutive behavior of the rock in which the gage is emplaced. This relationship is well understood for rocks with linear stress-strain behavior (Fossum, et al, 1976), but, for creeping rocks like salt, the relationship has yet to be determined. Thus, inclusion gage response in salt must be investigated fully before stress measurements from the WIPP in situ tests can be used for comparisons with computed stresses The calculations presented in this paper were performed as part of an investigation of inclusion stressmeter performance in salt. They focus on the strain gaged stressmeter (SGS) (Cook and Ames, 1979) and on a hypothetical solid cylindrical inclusion with variable stiffness Issues addressed include the effects of creep and the effects of gage stiffness on stressmeter output for various loading conditions. The

Jan 1, 1984

By R. B. Schluter, M. M. Fine

A process for winning copper from pelletized chalcocite concentrate without matte smelting and converting is under development at the Twin Cities Metallurgy Research Center of the U.S. Bureau of Mines. The new procedure includes a two-stage fluid-bed treatment in which the pelletized concentrate with 33% Cu and 7% S is first desulfurized to about 0.5% S in an oxidizing atmosphere, and then metallized by reduction with hydrogen. The reduced product is melted with flux to separate metallic copper from the gangue. The metal must be refined to remove residual sulfur and iron. The pelletizing of the fine concentrate into mini-pellets prior to fluid-bed treatment is an important feature of the process, because it permits shorter reaction time, decreases dusting, and facilitates subsequent processing.

Jan 1, 1972

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By C. R. Barker, D. A. Summers, H. D. Keith

Introduction Historically, the presence of methane has been a problem, mainly in and around the working areas of active coal mines, and only in these areas has drainage been considered. Drainage, where practical, has been achieved through the drilling of holes forward into the coal and the surrounding strata from the working area. These holes generaly have been short in length, although where methane drainage operations around a longwall face have been undertaken, the holes have had to be longer in order to adequately drain from the center of the face into the access gate roads. In recent years, attempts have been made to degasify the coal seams in advance of mining, without disruption of the mining cycle. This is done by drilling much longer horizontal holes through the coal in advance of the working area. Under the aegis of the federal government, methods have also been developed for draining coal seams of their methane content in advance of mining, but from shafts sunk from the surface, without using the active area of the mine as the location for the drill holes. Development of methane drainage has recently been encouraged by the potential use of the drained methane as a commercial energy source, with a need, therefore, to adequately organize a collection system, separate from mining the seam for coal. This has already been successfully accomplished, for example, in the Federal No. 2 mine of Eastern Associated Coal Corp. starting in 1975 (Johns). However, whether the system gains access to the coal through horizontal drilling from a pre- existing mine or via access through a separate shaft from the surface, long horizontal holes are required to adequately tap the methane reserve. It is to this regard-the actual drilling of the horizontal holes-that this paper is directed. It will examine potential benefits that may accrue, both in conventional horizontal hole drilling from a mine site underground, and also in drilling from the surface if a high pressure water jet drill is used to drill the degasification holes. Long Hole Drilling from an Underground Site Personnel from the Bureau of Mines have recently examined methods for conventional drilling of long horizontal holes to gain access for methane drainage. They have shown that it is possible (Cervik, Fields, and Aul) to drill out some 610 m using a conventional drilling system. Three types of bit were used in the program and by alternating between a drag bit, tricone bit, and plug bit, advance rates of between 0.6-3.6 m/min were achieved. Hole diameters varied from 7.6-9.2 cm in surface tests at bit thrusts of 1360 kg. A hole was then drilled and maintained in relative alignment within the coal seam for a distance of 640 m. Thrust levels had to be lowered to between 363-680 kg across the bit. Because the loads were smaller than those used in the surface trial, advance rates in the hole were of the order of 10-38 cm/min. The thrust level was lowered since it was found that the level of the thrust controlled the inclination of the drill so that, for example, a thrust of 363 kg caused the hole to incline downward, while at greater than 544 kg the hole inclined upward with the 9-cm-diam bit. Thrust levels increased 227 kg when the hole diameter was raised to 9.2 cm, although in such a case penetration rates in excess of 56 cm/min could be achieved. Horizontal Water Jet Drilling of Coal The University of Missouri-Rolla has recently undertaken research for Sandia Laboratories on the use of high pressure water jets as a means of drilling through coal. The initial experiment in this program called for drilling a hole horizontally into a coal seam from the side of a strip pit using water jets as the cutting mechanism. A very simple setup [(Fig. 1)] was used in this program and a 15-m hole was drilled at an approximate drilling speed of 1.2 m/min. The nozzle was designed so that the hole dimension was approximately 15 cm across [(Fig 2)] and the thrust was maintained at levels below 91 kg in moving the drill into the coal face. The system used was very crude and comprised a high pressure water jet drill enclosed within a 5.7-cm outer diameter galvanized water pipe to provide rigidity to the drilling system. This pipe sufficed to maintain hole alignment over the 15-m increment. While it is premature to make long-term predictions on ultimate applicability of this sytem to long hole drilling, certain inherent advantages of water jets can be delineated from research results and suggest considerable advantage to further research in development of this application. High pressure water was supplied at approximately 62 046 kPa from a 112-kW high pressure pump, with a 83 L/m flow through the supply line to the nozzle. The drilling system consisted of a nozzle rigidly attached to the front end of the galvanized piping. High pressure fluid was supplied to this nozzle through a flexible high pressure hose that fed from the nozzle back through the galvanized pipe to a rotary coupling attached

Jan 1, 1981

By J. H. Lightfoot, Stuart E. Buckley

DEEP drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.1 The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen4,5,6 and by others,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems.9-17 It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 lb. per sq. in. Thus, at pressures of 2500 lb. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 600°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduction. The combined effects of pressure and temperature on condensation and vaporization of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpretation of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate systems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21.22 it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has

Jan 1, 1941

By J. L. Wyatt

THE smelting of ilmenite to produce a slag rich in titanium, with pig-iron as a byproduct, introduces new concepts in electric smelting metallurgy. Titanium slags are characterized by low electrical resistance, thereby requiring a different type of electric furnace operation, and power supply sources substantially different from those encountered in normal steel melting and siliceous ore smelting furnaces. This paper describes special apparatus for determining specific electrical resistivity of titanium slags, and reports the values obtained on slags encountered in the process of smelting ilmenite ores. In an induction furnace under conditions approximating normal furnacing operation, 25 general heats and 6 special standardization and comparison heats were run. Results indicate relatively low resistivity. Resistivity depends primarily on slag composition, and, to a lesser degree, on temperature. During the summer of 1947 a cooperative project between the National Lead Co. and the Bureau of Mines was conducted at Boulder City, Nevada, in the Electrometallurgical Laboratories of the Bureau. The project involved smelting of ilmenite ores in electric furnaces, and has been reported in detail.' The author participated as a member of the staff of the National Lead Co. during the entire campaign. One outstanding characteristic of the titaniferous slags, their apparently excellent and variable electrical conductivity, was considered sufficiently important to warrant further study. Although little electric smelting of iron ores has been done in the United States, a certain amount of information is available for comparative purposes. Personal experience in smelting siliceous iron ores in electric furnaces furnished further information for comparison. In general, silicate slags are relatively poor conductors of electricity. Current flow during smelting operations may be maintained through a floating layer of coke on top of the slag bath, or through a bath of molten iron, beneath the slag. Silicate slags are not sufficiently conductive to furnish a path for current passage when normal furnace voltages are used. Experimental smelting of a silicate iron ore was undertaken for comparative purposes. A fluid melt was not obtained until the FeO content was reduced to 15 pct. The resistivity increased as the FeO content decreased, FeO compounds being the most conductive of the various oxides in such a normal slag system. The converse appears to be true in slags containing large percentages of TiO2. It has been found that titanium slags become molten with FeO percentages in excess of 30 pct, and that the conductivity becomes generally better as the FeO con-tent of the slag diminishes. This phenomenon was demonstrated in the furnacing operations at Boulder City. During the initial smelting period furnace electrodes could be held immersed several inches in the slag, with tap selectors set for a no-load voltage of 70 v. As the FeO content decreased, the furnace electrodes would "walk up," until at one point in the process the tips would break the surface and arc on top of the slag. This was undesirable since direct arcing caused losses of important flux additions. The slag compositions under study at that time were such that losses due to surface arcing sometimes caused viscous slags to be formed. Forcing the electrodes into the slag bath by manual control to prevent surface arcing resulted in excessive power input and lack of control. Suitable low voltages were not available. Measurement of the electrical resistivity of titanium slags at various operating temperatures and slag compositions was undertaken. It was believed that this information would be of use in the design of electric furnaces suitable for smelting ilmenite, with voltages, electrode sizes, and electrode spacing adapted specifically to titanium slags.

Jan 1, 1951