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By G. R. Mansfield

THE third year of Government exploration f or potash by the U. S. Geological Survey and-the U. S. Bureau of Mines under the authorization of the act approved June 25, 1926 (Public 424-69th Cong.) is drawing to a close. The results thus far obtained are thought to be sufficiently interesting and satisfactory to justify the presentation of a brief preliminary account of the work. REVIEW OF EARLIER EXPLORATION The general geologic similarity of the Permian basin of Texas and New Mexico to the potash field of Germany had long ago suggested the possibility of the presence of potash salts somewhere in that basin, but petroleum exploration was then making little headway there and the necessary data could not be obtained. The discovery by Udden in 1912 of potash in brine from the Spur well in Dickens County, Texas, was the first direct evidence of its presence. In 1915-17 the U. S. Geological Survey drilled a test well with standard tools at Cliff side near Amarillo, but failed to find potash. Nevertheless, an observer has been kept in the field, at first in cooperation with the Texas Bureau of Economic Geology but since 1922 by the Survey alone, to `secure data and samples from oil and gas tests. Since the discovery of oil in Reagan County in 1923 exploration by drilling has been rapidly extended to many parts of western Texas and southeastern New Mexico. The identification of the potash-bearing mineral polyhalite was first announced by the Geological Survey in June, 1921, the material having come from cuttings from the Bryant well in Midland County and the Burns well in Dawson County, Texas. Successive discoveries and announcements of similar purport aroused widespread interest in potash exploration, which culminated in the action by Congress already noted.

Jan 1, 1929

By E. S. Moore

THE Kolar gold field has been for a long time the most important gold-producing area of India. It is situated in the State of Mysore, southern India, and not far from the City of Bangalore. The productive field is about 3 miles long and in it a gold-bearing quartz vein varying in width from 1 in. to over 10 ft. is worked. The vein carries high values to great depths and many of the mines have paid large dividends. GEOLOGICAL FORMATIONS IN THE MOLAR REGION The rocks of the Molar region are pre-Cambrian in age and bear a close resemblance to some of the pre-Cambrian formations of America. The oldest rocks seen are basic lavas, now mostly altered to hornblende-schists, with which is associated some banded iron-formation; these rocks are similar to the Keewatin schists and iron-formation in the Lake Superior region. The schist is cut by the gold-bearing quartz vein. In certain parts of the area there is also a conglomerate containing pebbles of granite, jasper,, and schist. The matrix resembles a horn-blende-schist and is intruded by small granite dikes, which in some cases have been pinched off by squeezing of the rock. This has led Dr. W. H. Smeeth, Chief Inspector of Mines of Mysore, to whom the writer is greatly indebted for information regarding this area and for his hospi-tality while visiting the field, to regard this conglomerate as a breccia due to crushing of granite dikes in the schist. Dr. J. W. Evans has regarded the conglomerate as probably a squeezed glacial boulder clay. From analogy with pre-Cambrian conglomerates in America, the writer regards it as a metamorphosed rock similar to our basal Huronian conglomerate. However, the main bearing which it has upon the problem under discussion is the apparent fact that it is younger than the schist

Jan 3, 1918

By B. S. Norris, Charles R. Austin

The stresses which initiate deformation processes in metals are fundamentally important in the study of the mechanical properties of metals. A point of inflection in the load-elongation curves obtained for single crystals' has been rather too readily interpreted as a true yield point, and the critical resolved shearing stress on the plane of slip taken as a material constant. Even early work showed that the stress at this point varies with rate of loading, but it has not been generally appreciated that creep tests under static loads alone are suited for determining the existence or nonexistence of a yield point.* It has now been shown by Miller that single crystals of zinc3 when loaded statically begin to yield at loads too small to measure; as a result there is no case now known, apart from that cited in the present paper, in which a true critical stress for yielding has been demonstrated for single crystals of metals. The case of iron has especial interest: the existence of an upper and lower yield point and of an elongation at the yield point in ordinary iron and steel marks this substance as unusual, though the effects have been found to a very minor degree in other metals and alloys. $ Most alloys do not show such marked phenomena when appreciable yielding begins, and accordingly modern practice is to speak of the yield strength of such materials, a stress read from the load-elongation curve after elongation has begun, rather than yield point. The special behavior of iron suggests that it is more likely that single crystals of iron should have a true yield point than other metals. The study of the mechanical properties of metals and alloys requires a determination of the crystallographic mechanism of deformation, wlletller deformation proceeds by slip, twinning, or cleavage, or a combination of these, and a determination of the stresses that induce these modes of deformation. With this information, a study of the rates of work-

Jan 1, 1938

By B. S. Norris, Charles R. Austin

The stresses which initiate deformation processes in metals are fundamentally important in the study of the mechanical properties of metals. A point of inflection in the load-elongation curves obtained for single crystals' has been rather too readily interpreted as a true yield point, and the critical resolved shearing stress on the plane of slip taken as a material constant. Even early work showed that the stress at this point varies with rate of loading, but it has not been generally appreciated that creep tests under static loads alone are suited for determining the existence or nonexistence of a yield point.* It has now been shown by Miller that single crystals of zinc3 when loaded statically begin to yield at loads too small to measure; as a result there is no case now known, apart from that cited in the present paper, in which a true critical stress for yielding has been demonstrated for single crystals of metals. The case of iron has especial interest: the existence of an upper and lower yield point and of an elongation at the yield point in ordinary iron and steel marks this substance as unusual, though the effects have been found to a very minor degree in other metals and alloys. $ Most alloys do not show such marked phenomena when appreciable yielding begins, and accordingly modern practice is to speak of the yield strength of such materials, a stress read from the load-elongation curve after elongation has begun, rather than yield point. The special behavior of iron suggests that it is more likely that single crystals of iron should have a true yield point than other metals. The study of the mechanical properties of metals and alloys requires a determination of the crystallographic mechanism of deformation, wlletller deformation proceeds by slip, twinning, or cleavage, or a combination of these, and a determination of the stresses that induce these modes of deformation. With this information, a study of the rates of work-

Jan 1, 1938

By W. A. Doble

Opinions differ as to whether the water-wheel almost universally known as the Pelton type belongs to the impulse, the tangential, the reactive, the jet or the percussion class, or to a cross between two or more of these classes. The fact is, that for an almost infinitesimal part of a second the axis of the jet of water strikes the bucket of this wheel at a true tangent to its base-line. The percussion of the water, striking the bucket, imparts an impulse to the wheel, causing rotation; and generally the bucket is so shaped that the direction of the jet is

Jan 1, 1900

By H. C. Schultz, F. K. Middleton Hunter

Certain local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to develop usefully its full disruptive effect in hard ground. The individual blasts at Chuquicamata arc large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with 1,. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast. Present Liquid-oxygen Plant An experimental unit with a rated capacity of 75 liters per hour was erected during the latter part of the year 1926 to prove the effectiveness of L. 0. X. at this mine, its cost, and possible efficiency of large-scale storage of the liquid. With this experimental unit 200,000 tons of ore

Jan 1, 1928

By Donald W. Scott

This paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the *preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizeis and organic dyes, and 35 parts of water are added to 100 parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the over-spray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1948

By Donald W. Scott

This paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the *preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizeis and organic dyes, and 35 parts of water are added to 100 parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the over-spray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1948

By B. J. Shaw, R. Kossowsky, W. C. Johnston

High purity (99,95) Ni-51 wt pct cr eutectic alloy was unidirectionalty solidified at rates of 0.1 to 8 in. per hr. The resulting material was characterized by large grains, approximately 0.5 mm in cross section and extending through almost the entire length of the specimen, parallel to the growth axis. The eutectic structure of specimens the growth at -1/3 The per hr consisted of a continuous nickel-rich phase and chrome -rich lamellae approximately 2 thick, spaced about apart. Specimens were tested in compression at temperatures ranging from —196 to 850"C over which range the 0.2 pet yield strength dp -creased from 160,000 p si to 35,000psi, respectively. Swaging to 40 pet reduction in area, followed by a 30-min anneal at 1000c to remove residual cold work, increased the 0.2 pet yield to 260,000 psi at -196°C, dropping to 35,000 psi at 850°C. The increase in strength was attributed to a residual cell structure. The strength of the alloy could be rationalized by the simple rule of mixtures if one assumed that additional strength is derived front a size effect characterized by is petch equation IN recent years there has been increasing interest in dispersion and second phase strengthening in materials needed for high-temperature applications. inm role of structure on the mechanical The of such alloys has been well established of such some extent accounted for theoretically. and to of how the strengthening mechanisms due to fibers and lamellae operate has been reduced to its fibers form by the fabrication of composites of strong rods unidirectionally aligned in a From work on tungsten-fiber-reinforced copper, for example, it was established that the "Rule of Mixtures" could explain the strengthening.12 " some what more sophisticated technique for introducing strong fibers into copper matrix was used by Hertzberg strong Kraft3 who unidirectionally solidified the copper-chromium eutectic. The use of unidirectionally fied eutectics has advantages in that there are no matrix-fiber wetting problems and fine fibers are automatically aligned and uniformly fiber However, one Is restricted to a specific volume fraction of the second phase. Nevertheless, even though the volume fraction is fixed, the rod or lamella thickness, , can be varied by controlling the freezing interface velocity. Alternatively, the grown material may be worked down by swaging or rolling. Embury and Fisher, " using this approach, drew down pear lite in iron and studied the mechanical properties iron and that the yield strength, oy, was properties.proportional They that d was the wire diameter. It could be inferred that was also proportional to but the work hardening had to be taken into consideration at the same time. By varying the growth rate of the cadmium-zinc lamellar eutectic, Shaw'1 showed that was proportional to without the introduction of work hardening and suggested that the lamellar interface itself contributed to the strengthening of the composite. In this investigation we have evaluated the mechanical properties of the unidirectionally solidified fec-bec eutectic Ni-Cr. This eutectic was selected because it presented the possibility was selected beca temperature, and high corrosion resistant alloy, and also represented a hard-soft phase combination with two completely different slip systems. Specimens were tested in compression and tension up to 850°C and a detailed study of the micro structure as a function of plastic strain and temperature was carried out by light and electron microscopy. It was shown that the composite strength tested in compression can be accounted for by the simple rule of mixtures if one allows for an additional term representing the effect of Intereprese EXPERIMENTAL PROCEDURE 1) Unidirectional Solidification. Fig. 1 is a schematic drawing of the apparatus used to produce 0.2 in. diam by 12 in. long alloy ingots. The crucible tube is alumina, containing the charge which has been is swaged, or machined to 0.195 in. diam. The lower end of the tube is immersed to 0 .195in in.d iam. The upper end is supported by a 10 mil nichrome wire which lowers the crucible mil nic hr the] wire at a prescribed rate. Surrounding the furnace is a graphite susceptor into which a control thermocouple is inserted. The furnace is insulated with fiberfrax and enclosed in a quartz tube. There is a sliding seal at the bottom around the crucible and one on the top so that an atmosphere may be used for the sample and suscep tor. The power for the furnace is supplied from a 10-kw, 450 kc generator. The skin depth (the skin depth at which the field falls to l/e of its value at the outer surface) for graphite (p = 10 (j-ohm-cm) is 0.1 in. at this fre-

Jan 1, 1970

By C. B. Foster, S. I. Freedman, E. M. Jamgochian

Coal-oil mixture (COM) combustion technology is regarded by the US Department of Energy (DOE) as near term and Potentially applicable to existing utility and industrial steam generators and for injection into blast furnaces. From work done previously, it has been established that COM can be burned in existing boilers and blast furnaces. Therefore, the issues being addressed by the current DOE program are: (1) determination of best available technology to achieve environmentally acceptable long-term reliable operation and (2) determination of applications for which COM can be utilized economically. Some of the technological options have begun to be determined by projects already under way. However, many projects are still in the early stages of development.

Jan 1, 1980

By Frederic Becket

IN a recent article,1 which described the softening effect of columbium in plain high-chromium steels, the authors stated that their investi-gations had shown columbium to be also a particularly valuable inhibitor of intergranular corrosion in steels of the 18 per cent chromium, 8 per cent nickel type. It is the purpose of the present paper to record some of the results obtained through the introduction of columbium to the austenitic chromium-nickel steels. The damaging effects of this type of corrosion have become so widely known as to restrict considerably the applications of the steels under consideration, and therefore there is little question of the importance of the goal to be attained. Numerous contributions concerning the susceptibility of the aus-tenitic chromium-nickel steels to intergranular corrosion have appeared during the past few years, and among others who have dealt construc-tively with the subject are such well-known authors as Strauss and Houdremont of Germany, Hatfield of England, and Bain in the United States. Different theories have been propounded as to the cause of intergranular corrosion, and various remedial measures have been proposed, the majority of which involve the use of addition agents. Titanium is the addition agent at present most generally employed, as suggested by Houdremont and modified as described by Bain, Aborn and Rutherford.2 Little has been published on the effects of holding these steels for long periods at the relatively lower temperatures in the presence of

Jan 1, 1934

By Dwight K. Smith, Greg Carter

Studies have been conducted on The properties of many deep well cementing compositions to determine their Strength behavior over curing periods to 180 days at elevated tem-peratures and 3,000 psi pressure. This pressure results in essentially the .vat, compressive strength as that obtained with much higher pressures in ac-cordance with the findings of an API subcommittee ' These different compositions include API C1asses A, E, and F cements containig additives such as retarders, berrtorlite, heavy weight materials and pozzolans. All compositions except mixtures of Poz-zolrrrts and hydrated lime show from mild to severe degrees of strength lass over a temperature rang from -730 to 320" F after setting. Pozzolatl-time compositions actually gain in strength with time at these high temperatures. Other chemical find physical properties evaluated to observe their inter-relation.ship with Strength loss show very little correlation except in per-meability. As retrogression in strength increases, the permeability of set cement increases. X-ray difraction patterns on the set products indicate the formation of certain compounds having little or no strength value in those cementing compositions where strength loss was more severe. INTRODUCTION As a result of the growing trend toward deep well completions, a study has been made on the properties of the various cementing slurries presently in use at elevated temperatures and pressure. The strength of these compositions is of prime importance in selecting the most suitable material for use at high temperatures, to determine WOC time and the proper time to perforate with a minimum of shattering. Of primary interest in this investigation was the strength behavior of various compositions currently in use, and the effect of additives on cement after long periods of curing under severe conditions. Earlier investigators have pointed out that the strength of some cements will increase with increasing curing temperature to about 220 to 340" F, but at higher temperatures a loss in strength occurs at extended time intervals. Studies by the API Mid-Continent District Study Committee on Oil Well Cements' outlined a testing procedure whereby field conditions of temperature and pressure could be simulated in the laboratory.' It was observed that retarded cements undergo changes at elevated temperatures and some lose as much as 50 per cent of their early strength when cured at high temperatures. The scope of these tests was limited to curing periods of 1 to 28 days; additives were not covered in this study. Saunders and Walker' found that the use of additives influenced the strength behavior of cements at high temperatures, but studies were conducted only to a seven-day curing period. Ludwig and Pence' conducted an investigation of two types of cements under elevated pressures and temperatures in an effort to explain the causes of this loss in strength phenomenon. It was observed that with retrogression in strength there were other physical and chemical changes which took place as the cement aged. Today there are a number of cementing compositions available for use at well depths below 10,000 ft. Since all these earlier investigations were limited in curing time as well as the number and type of compositions studied, it was believed that a more extensive study should be conducted on the properties of cements at elevated temperatures, and this work should include those compositions actually in general field use at this time.

By M. B. Mirza, F. D. Wright

Models of photoelastic material were made to simulate a mine roof that had cracked over the edge of the pillars and at the center of the span. Models were restrained from moving laterally outward so they acted as flat arches. Uniform loading was approximated by loading the models along the bottom at eight points spaced equally along the span. It was found that for models with depth to span ratios of 1:3 to 1:6, the maximum stress at the top of the center crack could be calculated directly by the following formula: Elastic stresses in mine roofs composed of sedimentary beds are usually computed by assuming that the immediate roof bed acts as a fully restrained beam uniformly loaded by its own weight and by overlying strata. Very little work has been done to analyze stresses in roof beds or beams which contain vertical (normal to the span) or nearly vertical cracks. Yet every mining engineer has walked safely under roofs that show such cracks. As far back as 1933, Bucky' made model studies of the effect of vertical cracks on the behavior of horizontal strata. He did not make any analysis of the stresses but did show that a cracked beam will stand safely under certain conditions, and also showed that a beam restrained at the ends can crack over the supports and in the middle without collapsing as long as the ends of the beam are not free to move laterally outward. The beam, or rather, part of the beam, acts like a flat arch and supports itself by pushing outward at its supports. In 1941 Evans2 treated analytically the problem of a beam cracked along so many planes perpendicular to the axis of the beam that no tensile stress can operate. He named this type of beam a "voussoir-beam" by analogy to the voussoir-arch. In 1962 ~a~cocks~ modified Evans's solution by including the effect of the shear stress component of the resultant force at the abutment. This paper gives the results of a photoelastic study of the stresses in a beam containing vertical cracks in the center of the span and over the supports. A

Jan 1, 1963

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By Arthur Smith

THE Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district-the United Verde and the United Verde Extension-lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., . a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to? the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Wood chute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the . smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. This strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the vicinity of Allen Springs, at the south end of Mingus mountain and all within the boundaries of the Prescott national forest reserve.

Jan 3, 1924

Paper withdrawn from publication September 8,1977, after book was printed. Pages 258.272 are therefore omitted.

Jan 1, 1977

By C. S. Barrett, D. B. Masson

Martensitic transformations have been found in AgCd both upon cold-working at room temperature and cooling to lower temperatures. The crystal structures of the transformation products were found to be close-packed hexagonal in the first case and or-thorhombic in the latter. The transformation characteristics also were studied. Similar treatment of AuZn alloys failed to yield any transformation. THE literature on martensitic transformations of body-centered cubic metals and alloys indicates widespread instability of this structure at low temperatures, a tendency which merits further study. The body-centered cubic ß-phase of CuZn, for example, when it contained less than 42 wt pct Zn, was found by Greninger and Mooradian' and others' to transform on cooling to subzero temperatures to a phase that was tentatively considered to be tetragonal. Further work by Massalski and Barrett" demonstrated that cold work at low temperatures causes a partial transformation of ß CuZn of higher Zn content. The structures of the strain-induced transformation products were found to be different from those induced by simple cooling. Another well-known martensitic transformation among body-centered cubic phases is that of ß AuCd, first studied with X-rays by Olander,' then very thoroughly by Chang and Read.5,6 Here again transformation was found to occur both as a result of cooling and of strain. The alkali metals Li and Na, as well as certain Li-Mg alloys, also undergo transformation from their normal body-centered cubic structure, both on cooling and on cold-working. The phase AgCd, the subject of the present report, should be expected to behave quite similarly to CuZn for a number of reasons. It is the chemical analogue of CuZn, silver being directly below copper and cadmium directly below zinc in the periodic table. The size factors (percent difference in size) of the atoms, possibly a consideration in the stability of the ß-phases, are +3.1 in AgCd and + 4.2 in CuZn. Likewise the relative electronegativities of the two pairs of metals are about the same, CuZn possessing an electronegativity difference of 1.0 and AgCd one of 0.8. These values are from a table of electronegativities given by Darken and Gurry." The phase diagrams of the two systems around 50 atomic percent are similar, both possessing a disordered body-centered cubic phase, ß, at high temperatures and an ordered bcc phase, ß, at room temperature; however, the ß and ß' phases of AgCd are separated by a hexagonal phase, [, stable in the range 220-440oC, which has no analogue in CuZn. There has been confusion in the literature as to the structures of the ß' and [-phases. The phase diagram in the ASM handbook'" has the structures of the two phases interchanged; however, Hansen" reports the correct relative positions and Muldawer" verified that ß', the low-temperature phase, is body-centered cubic. Work by the present authors also

Jan 1, 1959

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;' it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.' Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By E. T. Turkdogan, M. T. Hepworth, R. P. Smith

The permeability of oxygen in 0 iron in the tempera-ture range 700" to 900 C and in 6 iron at 1450°C was determined by the rate of internal oxidation of iron, containing -0.1 pct Al. The solubility of oxygen in zone-refined iron was determined by equilibration with hydrogen-water vapor gas mixtures at 1450" and 1510°C; oxygen solubilities , for iron in equi1ibriu.rn with molten oxide, are found to be 66 and 83 ppm for these two temperatures, respectively. The diffusivity of oxygen in iron at 14500C3 as calculated from the permeability and solubility data, is (4.1 * 0.6) x 10 "B sq cm per sec. OXYGEN is one of the most common impurities present in iron or steel, mainly in the form of oxide inclusions. In the study of many metallurgical problems concerning solid iron, it is often desirable to know with a reasonable accuracy the solubility and diffusivity of oxygen over a wide temperature range. The solubility of oxygen in solid iron has been the subject of numerous studies yielding highly discordant results as seen for example from the literature surveys made by Meijering &apos; and Schenck et a1.&apos; As shown by Kitchener et aL3 and by Sifferlen, the high oxygen solubilities reported by many investigators are the result of oxidizable impurities which are often present in iron. In addition, there have been experimental problems associated with icaccuracy of oxygen analysis of iron containing less than 100 ppm 0. A number of studies have been made on the permeability of oxygen in a and y iron using Fe-Si, Fe-Mn, and Fe-A1 alloys in the internal-oxidation experiments.1&apos;2&apos;5&apos;6 However, no direct measurements have been made of the diffusivity of oxygen in iron. In the present work two sets of experimental measurements were made: permeability and solubility studies at 1450" and 1510°C and permeability studies only in the range 700 to 900°C. In both sets of permeability measurements slab-shaped specimens containing small predetermined amounts of aluminum in solution were exposed at constant temperature to gas mixtures of hydrogen, water vapor, and argon for varying times. These specimens were quenched, sectioned, and examined for oxygen penetration by metallographic observation of aluminum oxide particles which formed. From these data, it is possible to calculate the ratio of the diffusivity of oxygen in iron, D, to the equilibrium constant K for the reaction Hz(g) * O (dissolved in iron) = H,O(g). EXPERIMENTAL Permeability Measurements at 1450°C. An ingot of vacuum-carbon deoxidized iron containing 0.086 pct A1 was prepared, using commercial "Type lO4A Plas-tiron"; after hot rolling, specimens were machined into slabs a by 2 by 2 in. The impurity contents were: S, P < 0.002 pct; C, Mn < 0.01 pct; each of all other Usual impurities < 0.004 pet. The amount of oxide inclusions in this material, determined by a bromine-methyl acetate extraction, corresponded to about 20 ppm 0 in the iron which agreed well with the results of vacuum-fusion analysis. Each specimen was annealed at 1450°C for 1 hr in purified hydrogen, polished to a smooth surface, and then introduced into a controlled oxidizing atmosphere in a recrystallized alumina tube at 1450°C. The constant temperature zone (*3"C) was about 3 in. in length. The gas composition was controlled by mixing argon with hydrogen (using calibrated constant-head flow meters) and passing the mixture through a column of a mixture of oxalic acid dihydrate and 10 pct anhydrous oxalic acid, to establish a required water-vapor content in the gas mixture. The temperature of the oxalic acid dihydrate column was controlled by a thermostat. The total gas flow was in the range 800 to 1000 cu cm per min. The exit gas from the reaction tube was passed through a weighing bottle containing a desiccant, to cross-check the degree of water-vapor saturation, which for all experiments was about 97 pct of those derived from the data of Baxter and Lansing.1 For a typical experiment, a specimen was introduced into the furnace in a stream of dry argon and hydrogen. The specimen was then rapidly raised by a Pt-Rh alloy wire into the hot zone and allowed to reach the reaction temperature, at which time the oxidizing gas mixture was introduced. The oxygen potentials employed were sufficient to oxidize aluminum but not to cause liquid iron oxide to form. After a specified time, the experiment was ended by dropping the specimen onto a water-cooled copper block at the bottom of the reaction tube. The depth of the internally oxidized zone, hereafter called the "case", was determined by sectioning the specimen at right angles to the long direction. The section was then examined under a microscope equipped with a micrometer stage. In general, the oxide particles were fairly uniform in size and distribution, forming a reasonably well-defined interface between the oxidized and unoxidized region. A typical cross section as observed at X30 is shown in Fig. 1. A thermal macroetch was used in one selected specimen to delineate the case. A cross section of a previously oxidized slab was polished and reheated at 1450°C in a hydrogen atmosphere for about 10 min. Upon quenching, the surface relief shown in Fig. 2 was produced; causes of this effect are unknown. Permeability Measurements Below 900°C. A slightly

Jan 1, 1967