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By Henry Siegmann

HISTORY OF PRODUCTION AND USE In 1899 the consumption of fluorspar in the United States was reported as 16,000 tons. The invention of the open-hearth method of steel manufacture, plus the beginnings of a fluorine chemical industry, pushed consumption of fluorspar to 250,000 tons by 1918. In contrast to these consumption statistics of the past, the most recent statistics available (1972) indicate a total fluorspar usage in the United States of 1.352 million st (Table 15.4D.1). Fluorspar remains the world's cheapest source of fluorine, and its unique properties make the mineral the most desirable fluxing agent for steel refining. The linking of fluorine with carbon in the late 1930s resulted in the production of fluorocarbon, and constant growth in production over the years has formed the backbone of a strong fluorine chemical industry. For example, in 1972 it is estimated that total fluorocarbon production amounted to 2.113 million tons, and that, in this process, over 1.351 million tons of acid-grade fluorspar was consumed. The producers of primary aluminum long have been concerned about the fast dwindling reserves of natural cryolite. They found the solution to their problem by utilizing fluorspar for the manufacture of synthetic cryolite and aluminum fluoride. Nuclear weapons, as well as the growing number of peaceful uses for atomic reactors, constitute a market for uranium hexafluoride. This chemical and chlorine pentafluoride, used as an oxidizer with rocket fuels, are products that are as much a novelty as fluorocarbons were 25 years ago. Judging from past success in the field of fluorine chemistry research, it is safe to assume that the market for these chemicals will grow in the future. Three major industries account for the bulk of the fluorspar consumption: steel refining, fluorine chemical, and primary aluminum production. These industries have had a pattern of fabulous growth in the past, and their future plans point to a continuation of this pattern. It seems logical that the fluorspar usage also should continue its upward trend. Considering the growth of the fluorspar industry since 1899, and the obvious dependence on imports of fluorspar as a raw material, one of the most puzzling aspects of the past has been the apparent lack of coordination between fluorspar production and fluorspar consumption. A few authoritative voices have spoken out concerning the need to expand fluorspar production in order to meet consumption of the future. During World War II, the U.S. Government took positive steps in this direction by authorizing purchases at attractive prices for its "stockpile program." As a consequence, new fluorspar producing facilities were built, not only in

Jan 1, 1976

By Walter Renton Ingalls

In addition to the localities in which tin-ores have been found in Mexico, mentioned in my paper on the a Tin-Deposits of Durango," presented to the Institute in March, 1895,* the following should be recorded. I am indebted to Captain Henry Freeman, of Durango, for the notes as to these occurrences. In the Sierra de la Candela, west of the Sierra de Sail Frailcisco and El Promontorio (the Llano de Guatimape intervening between the two ranges), cassiterite is found in veins and stream-beds. The veins are narrow, and the ores have the same characteristics as those of Potrillos. They were exploited by miners from Coneto in 1882-86, the more extensive work having been done on the northern side of the mountains. In the Sierra de las Palomas, on the western edge of the Otinapa, ranch, about 25 miles W.N.W. from the Diablo mine in the Cacaria district, there are several small veins, of which the ore, gangue and country-rock are similar to those of the Cerro de los Remedios, near the city of Durango. The latter are essentially the same as the Potrillos veins. In the Cerritos del Olote, in the Murphy grant, about 50 miles W.S.W. from Durango, there are old mines, now partially filled. The veins are narrow and poor; the ore is highly ferruginous; the country-rock is rhyolite, with some granite; immense quantities of chalcedonic rubbish are strewn along the course of the veins. In the Cerro Blanco, overlooking the pueblo of Mezquital, 48 miles south of Durango, tin-ore is mined by the natives.

Jan 1, 1898

By A. E. Martin, Gerhard Derge

IF the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of diffusion, and electrical conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented as Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags of the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. REVIEW of LITERATURE In 1906 Aiken1 obtained a patent for a continuous process of producing iron electrolytically by passing a direct current through a bath of FeO-SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

T. A. Rickard, Denver, Colorado: The observations made by the author concerning the treatment of gold-bearing ores, deal with the subject only briefly and in a general way; but, coming from an authority, they invite comment. In stating the fact that a " finely-divided condition " is a necessary characteristic of ores containing free gold, the author must be refer ring to those mining districts only with which he himself is ac quainted. The statement would not be true of certain gold-mining regions in America and Australia. The ores of some Californian mines and the mill-stuff treated at certain of the mills of Clunes and Ballarat in Australia, and of Otago in New Zealand, contain the gold in a free but in a coarse state. Moreover, "reduction to fine sand and flour" is not required by certain ores, even though the gold be in a finely-divided condition. In such cases the gold becomes de tached from the quartz before the gangue has been pulverized into particles as small as those in which the gold occurs. The dry-crushing of free-milling gold-ores is onknown in the new mining regions of the world. It is not clear whether the author has in mind any European district in which such a process is in actual use. If he has, a description of the method and the results obtained would be very valuable. Dry-crushing is, other things being equal, twice as slow and twice as expensive as wet-crushing. In the case of free-milling gold-quartz it serves no purpose, since such ore does not carry sulphides which contain any large percentage of value, and which, by being slimed, may carry away part of that value. The dry-crushing of a free-milling gold-quartz would be considered an absurdity by an American metallurgist. If the ore contain "free gold only," why submit it to a further treatment, such as concentration, after its passage over the amalga mating-plate ? What does the author propose to concentrate ? Again, why anticipate the treatment of tailings by the McArthur Forrest, or some other process ? The satisfaction felt by a mill-man in saving gold by a subsequent treatment of the tailings from his mill appears to me to be like that of the man who shoots at a rabbit,

Jan 1, 1894

By R. R. Sayers

VENTILATION may be defined as the process by which vitiated air of an inclosed or partly inclosed space is continuously replaced by fresh air. Fresh air has been defined as invigorating pure air. Pure dry air at sea level contains the following gases:1 Analysis of Air at Sea Level PER CENT. Oxygen 20.94 Nitrogen 78.09 Carbon dioxide 0.03 Argon 0.94 Helium, krypton, neon, xenon, hydrogen, hydrogen peroxid, ammonia, ozone traces CARBON DIOXIDE LIMIT For many years carbon dioxide was used as an index of the purity of the air vitiated by the metabolism of people. It was, however, well known that the untoward effects produced on those exposed to such air was not due to the concentration of the carbon dioxide. It has been found that the untoward effects on the comfort and efficiency of those so exposed are due to the increased temperature and humidity. It has been found that men can breathe air containing many times the amount of carbon dioxide found in our worst ventilated theaters and assembly halls, which, according to Rosenau, do not contain above 0.5 per cent. carbon dioxide.

Jan 7, 1926

By Karl Sundberg, Allen Nordstrom

Interesting results were recently obtained in geophysical prospecting at the Questa mine of the Molybdenum Corpn. of America in New Mexico. This paper describes that survey, which was carried out during October and November, 1927, by the Swedish American Prospecting Corpn. It is hoped that the paper will make it possible for the mining man to form an opinion of the applicability of geophysical prospecting under difficult conditions, showing, as it does, the results when prospecting for small small orebodies with comparatively poor conductivity, in a region of rough topography. Some principles underlying electromagnetic prospecting not known to be published previously will also be given in an elementary way, with special attention to the general structure of the electromagnetic field. Geological. Conditions at Questa The property is situated in the Taos range of the Rocky Mountains in northern New Mexico. About this region, L. C. Graton says:' The main range is made up of Pre-Cambrian granites, gneisses and schists but in the vicinity of Red River igneous rocks of later age are present almost to the exclusion of the older series. These younger rocks are divisible into two groups. The older of the two, probably Pre-Tertiary age, is represented by large intrusive masses of monzonite porphyry, usually containing considerable quartz. The more recent group comprises intrusive and probably effusive dark-colored andesites and coarse andesitic breccias, some of which contain fragments of the monzonite; there are also flows of rhyolite and beds of rhyolite breccia. The evidence regarding the relative age of the andesite and the rhyolite is not wholly satisfactory, but there is little doubt that the andesite is the older. The ore deposits, although occurring more commonly in the monzonite porphyry than in the rhyolite, nevertheless are believed to be genetically related to the rhyolite. They certainly cut the rhyolite or andesite in places, and hence fall in the late Tertiary. The molybdenite at the Questa mine occurs in veins in the alaskite granite porphyry belonging to the older part of the Pre-Tertiary eruptives. Overlying the granite porphyry is the granodiorite, capping the granite

Jan 1, 1929

By H. R. Barnhurst

It would be a difficult matter to trace from the beginning the very few improvements made in the burning of fuels prior to 1860. Donbtless the crossing of the sticks of wood in building a mood fire early appealed to our savage ancestry as a means of expediting its effectiveness for their crude culinary purposes. Stones and andirons came later in assisting the admission of air to the under part of the fuel bed, while beacons and cressets, utilized metal bars as supports for the same purpose. It is probable that Tuba1 Cain owed his success to the use of bellows making possible the use of mixed fuel and charge upon a hearth. With the development of working in cast iron, grate bars came in, and they are still with us doing duty in every household and almost every art where heat is a factor. Little was done beyond these crude methods prior to 1860. With the advancement of knowledge came the fuel-gas producer, a natural child of the retorts employed in supplying illuminating gas. It is only within the last 15 years that the conclusion became general that complicated systems for saving heat would not remedy deli-. ciencies in its primary development, and within that time there has been great advancement in the means of producing initially a fire of high effciency, so that to-day we are moving rapidly toward both high development and high absorption, with the resultant of high efficiencies. In studying the subject of the availability of pulverized coal as a fuel, it may occur to ask, why has this not come up earlier? This, question would be naturally prompted by recalling the fact that Thomas Crompton's English patents upon his methods were issued to him nearly 40 years ago. A conclusive answer to this, however, is that Crompton at that time had very crude facilities for making what was at best a very imperfect pulverization of the coal, arid the expense of preparation mas very great. He does not seem to have been aware of the advantage of a thorough drying of the coal in the

Jan 1, 1914

By R. M. Brick, M. A. Williamson

Certain features of the response of copper and brass to deformation and recrystallization remain obscure. The textures obtained on rolled sheet are listed by Schmid and Boas1 as: No adequate explanation has been advanced for the presence of the secondary deformation texture of copper and its absence in brass or for the origin of the cubic recrystallization texture of copper.2 A recent publication3 attempted to rationalize the above empirically described annealing texture of brass on the basis of retention of the (110) [112] rolling orientation plus twinning about the central octahedral poles of the usual secondary (110) [115] orientation. The difierence in the textures of annealed copper as compared to 70-30 brass is also shown by the difference in the position of ears for drawn copper, at o° and go", as compared with drawn brasses, at 45o, for all compositions between oo-10 and 70-30.4 Data on indi- vidual crystals are as yet too few to permit of an analysis of these textures comparable to that of mild steel as made by Barrett and Levenson.5 Experimental Methods The materials studied included copper specimens cut from the central, equiaxed crystal portion of a tough-pitch wirebar; brass made from this copper and high-purity (99.99 per cent) zinc including alloys of 7 per cent, 15 per cent, 24 per cent, 29 per cent and 36 per cent Zn and large single crystals of 70-30 bras. Sections 1/4 in. thick of the cast polycrystalline copper and brasses were reduced 40 per cent by rolling, recrystallized to a common grain size of 0.045 mm. and then rolled directly to foil 0.002 in. thick. Hardness readings employing both the Vickers and Rockwell machines were taken at intervals during the reduction. For comparison, similar specimens were cross-rolled—i.e., turned through 90° for each pass—and comparable hardness data were secured. Finally sections from the single crystals of brass were cut to obtain the following initial orientations; these sections were rolled, hardness data secured and a complete micrographic record of structural changes obtained.

Jan 1, 1941

By R. M. Brick, M. A. Williamson

Certain features of the response of copper and brass to deformation and recrystallization remain obscure. The textures obtained on rolled sheet are listed by Schmid and Boas1 as: No adequate explanation has been advanced for the presence of the secondary deformation texture of copper and its absence in brass or for the origin of the cubic recrystallization texture of copper.2 A recent publication3 attempted to rationalize the above empirically described annealing texture of brass on the basis of retention of the (110) [112] rolling orientation plus twinning about the central octahedral poles of the usual secondary (110) [115] orientation. The difierence in the textures of annealed copper as compared to 70-30 brass is also shown by the difference in the position of ears for drawn copper, at o° and go", as compared with drawn brasses, at 45o, for all compositions between oo-10 and 70-30.4 Data on indi- vidual crystals are as yet too few to permit of an analysis of these textures comparable to that of mild steel as made by Barrett and Levenson.5 Experimental Methods The materials studied included copper specimens cut from the central, equiaxed crystal portion of a tough-pitch wirebar; brass made from this copper and high-purity (99.99 per cent) zinc including alloys of 7 per cent, 15 per cent, 24 per cent, 29 per cent and 36 per cent Zn and large single crystals of 70-30 bras. Sections 1/4 in. thick of the cast polycrystalline copper and brasses were reduced 40 per cent by rolling, recrystallized to a common grain size of 0.045 mm. and then rolled directly to foil 0.002 in. thick. Hardness readings employing both the Vickers and Rockwell machines were taken at intervals during the reduction. For comparison, similar specimens were cross-rolled—i.e., turned through 90° for each pass—and comparable hardness data were secured. Finally sections from the single crystals of brass were cut to obtain the following initial orientations; these sections were rolled, hardness data secured and a complete micrographic record of structural changes obtained.

Jan 1, 1941

By Keith Leonard Sutherland

THIS paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C. being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate -free.1,4 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. PURITY OF REAGENTS The xanthates were purified in the usual manner.1 Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes. This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. RESULTS The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when, zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1942

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By J. R. Schneider

INTRODUCTION Landowners in Texas for many years have freely granted, reserved and leased "oil, gas and other minerals" or interests therein. In recent years we have witnessed much litigation concerning what sub- stances should be included as "other minerals" within the phrase "oil, gas and other minerals," and this question has received the attention of numerous legal scholars. At the South Texas Uranium Seminar held in Corpus Christi, Texas, in September, 1978, Mr. William R. Dodson presented a paper dealing with this very subject and entitled "Uranium - Mineral or Surface? Who Owns It?" In his paper, Mr. Dodson reported on two recent Texas Supreme Court decisions, Acker v. a, 464 S.W.2d 348 (Tex. 1971) and Reed v. Wylie, 554 S.W.2d 169 (Tex. 1977). which held that the particular substance in question in each case is not a mineral within the phrase "oil, gas and other minerals" if substantial quantities of the substance lie so near the surface that production will entail the stripping away and substantial destruction of the surface. Since that time another chapter has been written in the Texas saga of "When is a Mineral not a Mineral?" and it is the intent of this paper to present an update of the Texas law. A review of the early Texas cases so ably covered by Mr. Dodson in his paper will not be repeated, except as is necessary to illustrate the evolution of the legal doc- trine which has been so aptly named "The Surface Destruction Test". BACKGROUND In order to appreciate the genesis of the problem, one must consider that oil and gas production commenced in Texas many years ago, Spindletop came in in 1901. As oil and gas became more valuable, land- owners with considerable frequency sold interest in the oil, gas and mineral estates in their lands, and reserved interest in the oil, gas and mineral estates in their lands when they disposed of their property. Due to the oil and gas background, and perhaps be- cause oil and gas was paramount in the minds of the parties, the traditional language employed in these grants and reservations was "oil, gas and other minerals" or variations thereof. There are literally hundreds of instruments employing this language constituting a link in the chains of title to thous- ands of acres of Texas land. In addition, there are thousands of acres of Texas land held by oil, gas and mineral leases, the primary terms of which have been perpetuated by production, containing similar language in their granting clauses. The severance of the mineral estate from the surface estate results in two separate and distinct estates, each having all of the incidents and attributes of an estate in land. with the surface estate being the serviant estate, and the mineral estate being the dominant estate and having certain easements in the surface estate to explore. produce and remove the minerals. Harris v. Currie. 176 S.W.2d 302, 305 (Tex. 1943). As observed by the court in the Harris case, this is because a grant or reservation of minerals would be wholly worthless if the grantee or reservor co~lld rwt enter upon the land in order to explore for and extract the minerals granted or reserved. Although the Texas law has recognized that an oil and gas lessee has the right to use so much of the surface as is reasonably necessary to produce the minerals. Warren Petroleum Corporation v. Monzingo, 304 S.W.2d 362, 363 (Tex. 1957), recent decisions of the Court have qualified this doctrine. In Getty Oil Company v. Jones. 470 S.W.2d 618 (Tex. 1971). Getty's pumpine, units were interfering with ones self-propelled sprinkler system utilized for irrigating the premises, and Jones sought to require Getty to install the-pumping units in cellars so that the sprinkler system could pass over them. In an effort to accommodate both the surface estate and the mineral estate, the court held (page 622) "...where there is an existing use by the surface owner which would otherwise be precluded or impaired, and where under the established practices in the industry there are alternatives available to the lessee whereby the minerals can be recovered, the rules of reasonable usage of the surface may require the adoption of an alternative by the lessee". Bearing in mind that the "reasonable use doctrine" grew up in the oil and gas industry involving sub- stances which can be produced by methods that do not destroy or deplete the surface estate, the question presented is whether the Texas courts will extend this doctrine to situations where claimants of "other minerals" seek to produce shallow deposits of iron ore, coal, lignite and uranium by surface mining methods which do destroy or deplete the surface estate? The surface destruction test has answered this question in the negative, at least as to iron. coal and lignite. However, the multitude of mineral estates in Texas which have been created by a grant. reservation or lease of "oil, gas and other minerals" will, doubtlessly, continue to fuel the fires of litigation. EARLY TEXAS DECISIONS In view of the evolution of the Surface Destruc- tion Test, an exhaustive review of the early Texas

Jan 1, 1980

By J. H. Moran, E. E. Finklea

The pressure build-up technique is a recognized method of determining permeability from conventional drillstem tests. In this paper an effort is made to extend such techniques to the interpretation of data obtained from the wireline formation tester. Such a study is necessary because of the differences, for this case, in the magnitude of the flow parameters (rate of flow, amount of recovered fluids) and in the flow geometry (flow through a perforation vs flow across the face of the wellbore, etc.) involved in the solution of the equations of flow for compressible fluids. The perforation is replaced by a spherical hole, and the effect of the borehole is neglected, so that the flow can be considered to be radial in a spherical co-ordinate system. Arguments are presented to justify this idealization. Assuming single-phase flow, general relations between pressure and flow rate are developed for a homogeneous medium. The study is then extended to permeable beds of finite thickness. It is shown that the early stages of pressure build-up tend towards spherical flow, while the later stages tend towards cylindrical flow. The thinner the bed, the more quickly flow approaches the cylindrical model. The prevalence of thin beds in practical work makes this analysis quite important. Cases involving permeability anisotropy are treated. INTRODUCTION From wireline formation tester operation, two types of data are obtained: (1) the nature and amount of recovered fluids, and (2) the pressure history recorded during the test. A number of papers have been written dealing with the interpretation of formation production on the basis of the recovered fluids.'.' In general, the methods described have been quite accurate for both high- and low-permeability formations. The present paper will deal with an analysis of the pressures observed. An analysis of the pressure build-up curves obtained in hard-rock country has already been attempted on the basis of the formula proposed by Hor-ner. Although this approach has met with success in many instances, some questions have been raised as to its validity. It is the aim of the present study to place the analysis of pressure build-up in the formation tester on a firmer basis, from which more detailed methods of interpretation can evolve. Because of the great differences between the operation of the wireline formation tester and the conventional drillstem test, modifications are necessary in the interpretation. The major difference relates to the flow geometry. Once the flow geometry has been established other features such as multiphase flow, skin effect, afterflow, etc., well described in the literature, can be introduced. It will be assumed that the mechanical operation of the formation tester is already known to the reader.6 t will suffice here merely to state that the tester provides the means for taking a relatively small sample of the fluid immediately adjacent to the borehole, and for recording the subsequent pressure response. In comparison with conventional drillstem tests, the time required for a satisfactory pressure build-up response is much shorter, because of the relatively small quantity of fluid withdrawn by the wireline tester. This feature is highly desirable in the case of low-permeability formations. For an analysis of the pressure response within the formation, three simple flow geometries are considered— linear, cylindrical and spherical. The spherical and cylindrical flow geometries are most pertinent to the formation tester; therefore, they will receive the major emphasis. Since the configuration of the borehole and the perforation made by the tester complicate the flow geometry, it is necessary to allow for them in the drawdown response. However, because of the volume of formations contributing to the pressure-response, the details of the perforation shape are unimportant in the build-up period. Since relatively small amounts of fluid are withdrawn from the formation, in contrast to a conventional drill-stem test, a study of the "depth of investigation" and the significance of drawdown as well as build-up data will be included. Because the "depth of investigation" will be shown to be rather large, the effect on the build-up curves of the finite thickness of the permeable bed is considered. It is this consideration that leads to the importance of cylindrical flow geometry. Also included is a discussion of permeability anisotropy and its effect on the interpretation of the tester results. The pressure curves recorded by the formation tester will follow two general patterns, depending upon whether the formation is of high or low permeability. Fig. I (a and b) schematically illustrates these two responses. In Fig. 1(a), the high pressure recorded during fill-up of the tool is essentially the pressure differential across the choke in the system. In Fig. l(b), the flow rate is

By Robert W. Pack

Sooner or later in the development of any natural resource it becomes highly desirable to know the quantity of this resource in the country as a whole, as well as of the part that is being developed, for the general course and conduct of the development work must be governed, to some extent, by the total supply available. An accurate estimate of the quantity of any natural resource is difficult to make; yet if one is diligent enough one can obtain a pretty accurate idea of the quantity of marketable timber, the acreage of tillable land, or the horsepower that may be developed from the streams, for these are things that may be measured. But any attempt to estimate the quantity of some mineral in the ground appears to enter the realm of imagination and it seems that the estimate can be nothing more than a blind guess. It may appear to be especially futile to attempt to determine the quantity of oil and gas that is available in the ground, for these minerals are so vagrant that even if the quantity now available should be known quite exactly, the quantity that will eventually be obtained may be much less, for certain losses in the extraction of both oil and gas are unavoidable, and just what these losses will be cannot be predicted. Though necessarily inaccurate, estimates of such mineral reserves are, however, of distinct value, for they summarize the existing knowledge of the deposits of the mineral and thus enable those who are interested in some industry that depends in one way or another on this mineral to formulate a rational commercial policy. Some time ago, when the price of gasoline suddenly rose in a rather spectacular manner, the writer was one of the U. S. Geological Survey geologists called upon to help to estimate the quantity of oil that could be obtained in the United States, for the fear had become widespread that perhaps the rate of increase in the price of gasoline was a measure of the rate of depletion of the supply of petroleum. It thus became his

Jan 1, 1918

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By James Howard

ON Aug. 25, 1911, a rail failed on the Lehigh Valley Railroad, causing a disastrous wreck. The surface of the fracture was in a plane at right angles to the length of the rail. There was a dark-colored, oval spot on this surface, located on the gage side of the head, representing the part of the rail which was the first to fracture. The nucleus of this spot showed that the fracture had an interior origin. Other fractures of this kind, the peripheries of which had not reached the surface of-the rail, presented surfaces having a silvery luster. The darkened surface of the present fracture was caused, doubtless, by the air having had access to it. This fracture was recognized as a fatigue fracture, of a modified type, its interior origin having been due to a component in the rail which is not usually present in cases of fatigue fractures. The metal next the running surface of the head of the rail was in a state of internal compression, this being the component not commonly met with in other cases, and which caused the fracture to have its interior origin. For the purpose of giving this modified type of fatigue fracture a specific name, for identification, the term "transverse fissure" was applied. No mystery was thought to attach to its formation, or to its development. The explanation of its occurrence was obvious in the light of common knowledge upon the behavior of steel under repeated alternate stresses. By reason of the state of internal compression at the running surface, the maximum tensile stresses in the head, under bending loads, were along an interior element. Here the tensile strains were higher than in the fibers more remote from .the neutral axis. Under such conditions the fracture of the rail would be expected to have an&apos; interior origin. A discussion of the subject of transverse fissures essentially becomes a discussion of fatigue fractures, since they are identical. The descriptive term employed, merely for the identification of this type of fatigue fracture, had the appearance of creating alarm. Apprehensions arose that a new phenomenon in the physical properties of steel had presented itself, the explanation of which was sought in every

Jan 11, 1917

Henry D. Hibbard, High Bridge, N. J. (Communication to the Secretary): There is one chemical factor which has not been considered in the author&apos;s tabulation of tests, but which is none the . less important because it cannot be practically estimated, and that is the element oxygen. This element has been, and probably will continue for some time to be, one of the great causes of the continual discrepancies between the chemical and physical properties of steel. Probably oxygen occurs, in important proportions, only in soft steel, such as that which we are now considering. In this steel its physical effect is to diminish tensile strength and elongation. The percentage of oxygen in the steel, under working-conditions that are as uniform as possible, is likely to vary inversely as that of the manganese, or perhaps, and more probably, it may bear even an inverse geometrical ratio to the manganese-content. At all events, to follow the author&apos;s plan, the line representing the loss of strength due to oxygen is probably a curve. Plotted by itself, the line would probably be straight; that is, the decrease in strength would be proportional to the increase in oxygen, but if the results were superposed on the percentages of manganese, they would give a curve, because the percentages of oxygen increase faster than those of manganese decrease. Were the oxygen-line to be developed and added to the diagram, it would seem that the manganese-line should then be straight. Due allowance for the effect of oxygen, therefore, would modify two features of the paper. It would increase the figure for the strength of pure iron from 38,000 to about 45;000 pounds per square inch, and it would straighten out the manganese-curve. The manganese-line in the paper is curved between 0.50 and 0.20 per cent. Above 0.50 per cent. it is straight, which may be ascribed

Jan 1, 1893

By D. G. Westlake, U. F. Kocks

WHILE single crystals of most materials with cph lattice structure show essentially unlimited ductility, polycrystalline specimens of the same materials exhibit the entire range of ductilities. A difference between the ductility of single crystals and polycrystals may be associated with the special stress concentrations to be expected, for example, at the intersections of slip bands or twin lamellae with grain boundaries. Whether such stress concentrations prove catastrophic depends on the cleavage strength of the material, the size of the stress concentrations, and the speed with which they are formed. Thus, the ductility may vary in degree from material to material. Another possible reason for differences in ductility between single crystals and polycrystals is that a sufficient number of independent deformation modes must be available to insure compatibility between the macroscopic strains in neighboring grains.&apos;&apos;2 This criterion is often taken to be a necessary condition for any polycrystal ductility whatsoever, not as one that determines different degrees of ductility; thus, a material with an insufficient number of independent deformation modes would have to be brittle as a polycrystal. The "sufficient number" is five if every grain is to accommodate arbitrary shape changes ("von Mises criterion "). We should like to argue that fewer than five independent modes may be sufficient to satisfy compatibility conditions; and that the internal stresses set up when the plastic strains are not compatible reach the theoretical fracture stress only after a significant amount of macroscopic strain has taken place which may vary in magnitude from case to case, allowing an influence on the degree of ductility. Experimental evidence for these statements is taken from the following review of the number of independent deformation modes observed in the various cph

Jan 1, 1968

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10&apos;&apos; atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10&apos;&apos; to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein&apos; reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By AIME AIME

MONDAY evening a reception, supper and bridge in honor of the guests of the Woman&apos;s Auxiliary was given by the New York Section in the Engineering Woman&apos;s Club. After supper, tables were made up for bridge. Some tried jig-saw puzzles, while others merely visited. On Tuesday morning the annual business meeting was called to order by President Bassett. Mrs. Bassett read a note from Mrs. Hoover regretting her inability to be present, and then gave her welcome and message: It gives me much pleasure to welcome you in this annual meeting, and I hope you will be able to come next year, and those who are not able to come this year I hope will be here next year.

Jan 1, 1933