Search Documents

By E. T. Dumble

The history of the several petroleum deposits of Texas and Mexico, or of the sediments in which they now occur, if the deposits are not indigenous to such sediments, is known in a general way only, but it nevertheless casts strong light on the conditions surrounding them and is of great importance in the search for and exploitation of them. The petroleum deposits of Texas are separable into two main divisions: 1. The deposits of northwestern Texas, which are directly connected with the Oklahoma fields to the north, and have no representatives at all in the Mexican area. 2. The deposits of the coastal area, which extend into Louisiana on the east and connect with those of the Mexican coast to the south. Early in the Pennsylvanian period a series of bituminous shales and limestones were laid down over a broad area in Texas, Arkansas, and Oklahoma. These are known as the Bend series in Texas, the Caney shales in Oklahoma, and the Fayetteville beds in Arltansas. Following their deposition an uplift occurred, forming the Lampasas geanticlinal, which runs northeastward from the old Paleozoic land area of the Llano region toward Red River. The Bend series is petroliferous in places and has furnished a few producing wells on each side of the Lampasas uplift. This uplift forms the barrier and dividing line between the two divisions of the Texas petroleum deposits. To the west of it, in waters which were the southcrn extension of the interior continental seas, in connection with the sedimcnts and coal beds of the Pennsylvanian and Permian, great quantities of petroleum were deposited either as oil or as "potential petroleum." These sediments have been subject to very slight disturbance, and only very gentle folds are found, with no signs of volcanic action in any part of the area. The conditions, therefore, indicate that the greater part, if not all, of the oil in this area is indigenous to the beds in which it is found. East of the anticlinal the oldest beds which appear in contact with the Bend are the Trinity Sands of the Lower Cretaceous. No evidence has

Jan 1, 1916

By Jonathan G. Price

Silver-copper-lead deposits In Precambrian, Permian, and Cretaceous red-bed sequences near Van Horn, Texas, have the following features In common: (1) mineralization controlled by steeply dipping fractures in sandstones, (2) lack of ore in overlying and interbedded limestones, (3) absence of igneous intrusions, (4) sulflide ores without typical hydrothermal gangue minerals, and (5) associated arsenic, molybdenum, zinc, and cadmium but not gold. Ore was probably deposited along fractures by reaction between low-temperature, oxidizing, metal-rich ground waters and sulfide-bearing waters or rocks. Detailed mapping and studies of fracture patterns indicate that mineralization occurred during Basin and Range extensional deformation, thereby postdating major Trans-Pecos igneous activity.

Jan 1, 1984

By W. K. Hartley

INTRODUCTION AND HISTORY The Kimberley Division of De Beers Consolidated Mines Limited includes four underground mines in Kimberley viz. Dutoitspan, Bultfontein, De Beers and Wesselton Mine and two outside mines, viz. Finsch, an opencast operation and Koffie- fontein, an underground operation. Figure 1 is a map of the Kimberley district showing the location of these mines. Finsch is 150km west of Kimberley and Koffiefontein is 80km south of Kimberley. The head office of the De Beers Company is in Kimberley. The diamond sorting and trading companies for diamonds produced in South Africa are also in Kimberley. Diamonds were first discovered in the Kimberley area at Hopetown in 1866 on the banks of the Orange River. This, and later finds, triggered the start of the great "Diamond Rush". In 1870 the Jagersfontein (now closed) and Dutoitspan pipes were discovered, followed by those at Bultfontein, De Beers and Kimberley Mine (now closed) in 1871, Koffiefontein in 1880 and Wesselton in 1891. Finsch Mine was a more recent discovery in 1961. Finsch, due to go underground in 1986, and Koffiefontein, are fully self-contained with their own treatment plants, housing, services etc. The four Kimberley mines deliver ore by conveyor to a central treatment plant and use joint ser- vices. ,+lining is presently carried out mainly by Block Caving which has replaced the earlier Chambering method. De Beers Mine, on a limited scale, and Wesselton Mine have recently started to use Sub-Level Caving, and both Bultfontein and Du- toitspan are scheduled to use the same method at a later date. The combined ore tonnage produced by the Kimberley Mines is 17 400 tons per day, Koffiefontein 12 000 tons per day and Finsch Mine 17 000 tons per day. THE EVOLUTION OF MINING METHODS Initially, the open-cast mining was carried out to as great a depth as safety would permit. In the early stages of open-cast mining, the Kimberlite was removed in horizontal slices from levels 13m to 20m apart. The rock broken in the workings was raised to the surface by means of endless rope haulage inclines. As lower levels were attained these rope haulages were replaced by aerial hoists, inclined shaft haulages or inclined skip-ways. These methods were dependent upon the strength of the unsupported pipe walls, which became increasingly unstable with depth and a system was adopted whereby the ground mined in open excavations was tipped down passes to tunnels connecting with vertical hoisting shafts sunk in the country rock. As work in the open pit became more and more impracticable due to extensive falls of ground, this system was replaced by a combination of open-cast and underground mining, and eventually by wholly underground methods. Chambering With the advent of underground mining, a system known as "Chambering" (or "Inclined Chambering") was evolved. It was essentially a combination of shrinkage stoping and caving, whereby advantage was taken of the high pressure exerted by the loose rock that had accumulated in the open excavations due to the collapse of the pipe walls. This mining method was introduced around 1890 and was successfully employed, with little change, up to the early nineteen seventies. In this system each mine was served by a main hoisting shaft situated about 300m in the country rock. Main haulage cross cuts were driven from the shaft to the pipe at 200m (600ft) vertical intervals. A sub-vertical shaft, situated close to the pipe provided access to the working levels. Chamber levels were established from the sub-vertical shaft at 13m (40ft) intervals. See figure 2. On each of these levels successive 6,8m wide “cuts" were mined out across the pipe, from one rock contact to the other, and extended vertically to the footwall of the level above. Every 6,8m cut was made up of a chamber and a "back-pillart1, each approximately 3,401 wide. The chamber was mined by overhand shrinkage stoping. The levels were carried "en echelon", with each chamber on a level approximately three cuts ahead of the chamber on the level

Jan 1, 1981

By G. R. Countryman, G. H. Thomas, I. Fatt

Procedures are described for scaling up turbulent friction pressure drops of inelastic fluids and laminar friction pressure drops of inelastic/elastic fluids in circular ducts. The laminar scale-up calculation method does not require the use of arbitrarily defined flow models, and can be performed directly from laminar capillary viscometry data, or by means of a numerical solution of the integral equation for Poiseuille flow, inputing true shear rate-shearing stress data from other simple shearing experiments. e.g. Couette and plane Poiseuille flows. The turbulent scale up procedure, based on the Dodge-Metzner correlation for inelastic fluids, requires evaluating the characteristic rheological parameters at the existing wall stress under laminar flow conditions. Since the wall stress is the quantity sought in a pipe flow scale-up problem, a trial-and-err or solution is indicated, and therefore a calculation method has been developed and programmed for a medium-size magnetic-drum-memory digital computer. Laminar flow data from other somces may also be adapted to this turbulent scale-upmetbod for inelastic fluids. Comparisons between predicted and experimentally observed friction losses for generalized Reynolds numbers ranging from 3 — 32.000 indicate an error band width of less than 10 per cent in circular tubes ranging in size from 0.5 to 1.89 in. in diameter. INTRODUCTION Considerable effort has been devoted to the problem of establishing an accurate procedure for predicting the laminar and turbulent flow behavior of non-Newtonian materials in pipes from data obtained with small scale laboratory or pilot plant equipment, as evidenced by the variety of reviews on the subject.1-3 Although there does not appear to be a universally accepted scale-up method for laminar flow, the various methods currently employed can be divided into two principal categories depending upon whether a functional relationship between shear rate and shearing stress is assumed, or whether a generalized correlation is adopted. The methods of Hedstrom4 and of Weltmann are typical of the first category, while the generalized correlation of Metzner and Reed6 illustrates the second category. Under appropriate conditions either approach yields a reasonably satisfactory description of laminar flow behavior. In contrast, the prediction of non-Newtonian transitional and turbulent friction losses is much more complex. For example, certain types of materials have been observed to sustain laminar flow at much higher flow rates than Newtonian liquids. When turbulence does develop, the level of agitation is damped to such an extent that the friction factor is lower than that of the original low viscosity Newtonian medium. Extremely broad transition regions and "diameter effects" have also been noted in the turbulent flow of certain chemically complex materials.' Aside from the latter complications, which are attributed in part to viscoelasticity, the existence of a variety of scale-up procedures for predicting transitional and turbulent friction losses is due principally to the chioce of viscosity parameter used in the definition of the Reynolds number. In contrast, Dodge and Metzner have demonstrated that the friction factorReynolds number relationship for inelastic fluids can be satisfactorily generalized provided the fluid property parameters are evaluated at the existing wall shearing stress.* However, the quantity usually sought in a pipe flow scale-up problem is the wall stress, and hence a trial-and-error procedure is required when dealing with non-power law materials. In this report we discuss two calculation methods: (1) for determining the wall stress, and hence the friction pressure drop, for inelastic fluids under conditions of turbulent flow by means of an iterative procedure, and (2) for predicting laminar friction pressure drops without recourse to arbitrarily defined flow models.

By C. H. Herty

During the past few years frequent reference has been made to a certain type of iron known generally as "bad iron," "dirty iron," etc., both by steelmakers and producers of iron castings.' Open-hearth operators have claimed that such iron was entirely within the specified limits as to ordinary analysis but it was difficult to make good steel from it. It has been suggested that unreduced material in the iron is responsible, also that most trouble is experienced with the iron when the blast furnace is delivering a product whose analysis is more or less variable. Other reasons suggested are the use of scrap or borings, unsintered flue dust in the burden, a cold hearth, too high a proportion of unsuitable grade of ore, or the form of the carbon in the iron. Accordingly, a subcommittee was appoint at the fall meeting of the Open-hearth Committee of the Americ m Institute of Mining and Metallurgical Engineers held in Pittsburgh in October, 1926, to investigate the reasons for the occurrence of this bad iron and suggest methods for preventing its appearance. This committee enlisted the cooperation of the U. S. Bureau of Mines Experiment Station at Pittsburgh in undertaking a study of pig-iron quality as affecting the open hearth. The following is a report of the findings to date: Method of Testing Inasmuch as a "spell" of dirty iron occurs without warning and may be of short duration, it was deemed advisable to attempt to simulate the conditions existing before and during such a period and compare the quality of the steel made with the normal and with the dirty iron. The Bourne-Fuller Co., of Cleveland, which has a single furnace that supplies

Jan 1, 1929

By L. D. Lamont, W. C. Muehlhof

Throughout the anthracite industry's history, the problem of handling and disposing of refuse material has been one of major importance. In the early days of the industry's activities, only the large sizes of anthracite were satisfactory for market requirements and the smaller sizes were deposited as refuse. As time went by, more efficient coal-burning equipment was developed and a market demand was created for the finer sizes of coal. This demand made it possible to recover marketable coal from banks deposited as refuse in the earlier days of mining. The same condition holds good today and we can see a definite trend toward the objective of utilizing the No. 4 and No. 5 buckwheat sizes. Under present conditions, we know that a limited market exists for No. 4 and 5 buckwheat; we know that the finer sizes of anthracite can be burned as pulverized fuel; we know that these fine sizes can be processed and sold as briquettes, and we also know that the heat content of these fine sizes of coal is comparable with that of the sizes now merchandized. Therefore, it should be the objective of the industry to conserve these fine sizes of coal in such manner that if and when processing facilities are developed, and market demands exist, the material can be salvaged and made available to meet these demands. From the standpoint of economical future reclamation, the ideal method of disposing of refuse containing the finer sizes of coal is to deposit it in banks separate and apart from other breaker refuse. By this procedure, the minimum amount of material will be processed in future salvage operations to recover the No. 4 and No. 5 buckwheat sizes. Many collieries in the anthracite region are operated under leases that have a specific term. These lease agreements provide that, upon expiration of the lease by term, exhaustion or otherwise, the ownership of the refuse material reverts to the lessor. Therefore, a question was raised in the minds of these operators: Why should I assume the expense of such procedure when I have no assurance that I will benefit by the future processing and sale of these fine sizes? Under present conditions, the answer to this question is not one of choice but of necessity, as restrictions imposed by legislation make it mandatory on operators of preparation plants to take necessary steps to properly treat silt-laden waters before permitting them to enter the streams. By reason of these restrictions, the disposal of fine sizes becomes a secondary rather than a primary operating consideration, and the procedure for disposing of this refuse becomes a matter of choice governed principally by topographical and geographical conditions. Methods of Handling Refuse There are three principal methods of handling and disposing of fine-size refuse; namely:

Jan 1, 1947

By W. C. Muehlhof, L. D. Lamont

Throughout the anthracite industry's history, the problem of handling and disposing of refuse material has been one of major importance. In the early days of the industry's activities, only the large sizes of anthracite were satisfactory for market requirements and the smaller sizes were deposited as refuse. As time went by, more efficient coal-burning equipment was developed and a market demand was created for the finer sizes of coal. This demand made it possible to recover marketable coal from banks deposited as refuse in the earlier days of mining. The same condition holds good today and we can see a definite trend toward the objective of utilizing the No. 4 and No. 5 buckwheat sizes. Under present conditions, we know that a limited market exists for No. 4 and 5 buckwheat; we know that the finer sizes of anthracite can be burned as pulverized fuel; we know that these fine sizes can be processed and sold as briquettes, and we also know that the heat content of these fine sizes of coal is comparable with that of the sizes now merchandized. Therefore, it should be the objective of the industry to conserve these fine sizes of coal in such manner that if and when processing facilities are developed, and market demands exist, the material can be salvaged and made available to meet these demands. From the standpoint of economical future reclamation, the ideal method of disposing of refuse containing the finer sizes of coal is to deposit it in banks separate and apart from other breaker refuse. By this procedure, the minimum amount of material will be processed in future salvage operations to recover the No. 4 and No. 5 buckwheat sizes. Many collieries in the anthracite region are operated under leases that have a specific term. These lease agreements provide that, upon expiration of the lease by term, exhaustion or otherwise, the ownership of the refuse material reverts to the lessor. Therefore, a question was raised in the minds of these operators: Why should I assume the expense of such procedure when I have no assurance that I will benefit by the future processing and sale of these fine sizes? Under present conditions, the answer to this question is not one of choice but of necessity, as restrictions imposed by legislation make it mandatory on operators of preparation plants to take necessary steps to properly treat silt-laden waters before permitting them to enter the streams. By reason of these restrictions, the disposal of fine sizes becomes a secondary rather than a primary operating consideration, and the procedure for disposing of this refuse becomes a matter of choice governed principally by topographical and geographical conditions. Methods of Handling Refuse There are three principal methods of handling and disposing of fine-size refuse; namely:

Jan 1, 1947

By H. B. Bell, P. C. Lidster

A study has been made of the use of ThO2-Y2O3 solid electrolytes to determine activity of chromium in Fe-Cr and Ni-Cr alloys in the temperature range 1300° to 1700°K. This method has been shown to give results which agree with the best vapor pressure measurements. SEVERAL investigations1"5 have been made of chromium activities in Fe-Cr alloys. Most of these have been made by vapor pressure measurements using knudsen cell techniques while one has been made using gas equilibration with H2/H2O gas mixtures. In the present investigation electromotive force measurements have been made on this system using a thoria yttria solid electrolyte. This system was -chosen to establish the technique of measurement at low oxygen potentials, before extending it to Fe-Ni-Cr alloys. The cell used was Pt Cr • Cr2O3 ilThO2 • Y2O3 llalloy • Cr2O3 IPt Since the oxygen pressure of the chromium-chromic oxide mixture lay in the range 10"19 to 1027 atm in the temperature range investigated, thoria yttria electrolytes were used. It was soon found during the investigation that considerable care was required to prepare satisfactory electrolytes and a study was made to find the best method of preparing pellets of TI1O2-Y2O3 solid solution of as near theoretical density as possible. Various compositions in the range 2 to 15 mole pct Y2O3 were studied but the experimental measurements were made with electrolytes containing 4 to 5 pct Y2O3. The method of preparation finally adopted was to use thorium oxalate and yttria as raw materials. The thorium oxalate was decomposed at 900°C for 6 hr to give a reactive powder. This powder was then mixed with the appropriate amount of yttria and ground in an agate mortar for about 4 hr. The powder was moistened with absolute alcohol as a lubricant and pressed in a metal die at a pressure of 7 tons per sq in. The pellets were then heated at 1100°C for 24 hr followed by 24 hr at 1250°C. After this firing cycle the material was reground and repelleted and again fired at 1100° and 1250°C followed by heating for 7 days at 1600°C. It was found in later experiments that a further firing of 4 hr at 2000°C improved the density further and gave pellets of only 2 pct porosity. After firing, the pellets were polished on emery paper and finally with the 2 µ diamond paste. The polishing was followed by a final firing of 24 hr at 1500°C. Investigation showed that this final treatment minimized reaction between the electrolytes and chromium oxide. It was believed that this was because of a lowering of the surface energy of the electrolyte surface. Two types of investigation were carried out to check that the pellets were satisfactory oxygen ion elec-

Jan 1, 1970

By H. E. Stauss, E. I. Salkovitz, F. W. von Batchelder

EXISTING information regarding the structure of a spherulite in nodular cast iron is based on optical studies. According to these data, a nodule consists of an aggregate of graphite crystallites radiating from the center, with the closely packed basal planes at right angles to the radii. The c axes lie along the radii. This view faces some uncertainty in the fact that the c axis does not represent the accepted direction of fastest growth in graphite. To supplement the optical information, X-ray studies have now been made. The principle used was to screen the nodule in greater part from the X-ray beam and expose only a minor cap. As successively larger portions of the nodule were introduced into the X-ray beam, any differences in the X-ray patterns could be observed. Such photographs have been taken with chromium radiation and a Laue camera. The graphite nodule itself, about 0.010 to 0.025 in. in diam, was mounted with vaseline on a micrometer screw for control of the linear motion. The nodule rotated about 45" each time that it was translated linearly. The nodules were obtained from magnesium-treated hypereutectic iron by electrolytic solution of the iron in hydrochloric acid. In Fig. la is shown the pattern of the thinnest cap examined. In Fig. lb is shown the pattern of the same nodule moved 0.003 in. farther into the X-ray beam, and rotated 45" at the same time. Figs, la and lb indicate incomplete circles for graphite (the two outer circles arise from graphite) with the side arcs much weaker than the top and bottom ones. The arcs obtained are themselves not continuous in intensity but vary with maxima of intensity some 15" and 30" apart. The structure of the nodule that would give rise to such a pattern can be explained as follows. Basically the nodule consisted of small crystallites. The discontinuous character of the diffraction rings demonstrates that the nodule was not composed of randomly oriented crystallites. The strong vertical reflections and the weak lateral reflections show that the reflecting planes were roughly normal to the radii. The absence of sharp reflection spots suggests that the nodule did not contain large crystals. The sharpness of the diffraction rings in their radial direction shows that the variations in intensity along the arcs were not the result of line broadening resulting from extremely small crystals. In the diffraction patterns two rings corresponding to graphite were found. The third and inner ring in the figures originated in the vaseline. The graphite rings correspond to the a and ß lines reflected from the basal planes, showing that the radii of the nodules are the [0001] direction normal to the basal planes of graphite. The picture of the structure that is formed is, therefore, one of aggregates of crystallites. Within each aggregate the c axes of the crystallites tend to align themselves in the radial direction of the nodule, although these axes deviate somewhat in direction by a continuous variation of angle. Correspondingly the basal planes of the graphite crystallites are generally normal to the radii. It is a pleasure to acknowledge the assistance of M. C. Bloom and R. P. Dunphy of this laboratory.

Jan 1, 1952

By Strathmore R. B. Cooke, Marcus Digre

That calcium will activate quartz for flotation with anionic collectors such as soaps has been known for a number of years,12'3 and the method has been applied to the concentration of various iron ores4 5 6 as well as to other materials. Clemmer gives the permissible pH range for the activation of quartz by calcium as between 9.5 and 12.5 with an optimum value of 11.0, and Hertzog7 has determined the calcium abstraction of iron ores and of Ottawa sand, but otherwise little quantitative data are available. The purpose of the present investigation was to determine those conditions under which dilute solutions of calcium chloride will activate quartz for anionic flotation and to determine the amount of calcium ion adsorbed by quartz. Those variables, the influence of which was primary, such as calcium, sodium, and hydrogen ion concentrations, were studied. Other factors which influenced the results are discussed in the description of the experiments. Three different experimental methods were used to determine the activation of the quartz. The first method was to treat a sample of ground, deslimed quartz with solutions of calcium chloride and sodium hydroxide, and to determine the calcium adsorbed by chemical analysis of the solution. Advantages are that a direct value for the amount of calcium adsorbed is obtained, and introduction of a collector which may affect the adsorption is avoided. The difficulty is to determine the extremely small differences in the calcium concentrations before and after the abstraction. The second method was to determine the activation of the quartz by observing the contact angle obtained on pressing an air bubble against the polished surface of a piece of quartz immersed in a solution of calcium chloride, sodium hydroxide, and sodium oleate. This is the well-known "contact angle" method. The third method was to determine those conditions under which an air bubble will pick up quartz particles immersed in a solution of the desired reagents. Disadvantages common to the sec- ond and third methods are that introduction of a collector is necessary to obtain bubble contact with the mineral; very small quantities of contaminant can give erroneous results; and no information is obtainable concerning the amount of calcium adsorbed. Advantages are that tedious analyses, which at best give approximate results, are avoided, and the conditions, especially for the third method, closely simulate those of actual flotation. Although the most consistent results were obtained with the third method, this paper describes the techniques used and the results obtained from each of the three methods. Distilled water and analytical grade reagents were used throughout except where otherwise stated. Between tests all glass articles were cleaned with a chromic-sulphuric acid mixture and sodium hydroxide. Abstraction Method The raw material for the tests was Ottawa sand sized between 14 and 28 mesh. Batches of 500 g of this sand were dry ground for 1 hr in an Abbe porcelain mill with 2700 g of quartz pebbles. The batches were split down to samples weighing approximately 30 g, and the weight of each sample was adjusted to exactly this value.

Jan 1, 1950

By J. C. Bartlett

The following discussion was suggested by an experiment of Mr. Krom, the Manufacturer of air-jigs, to illustrate the superiority of air over water as a medium of concentration. The paper is written in the interest of no system of concentration, but simply to test the experiment, and, perchance, to add something to the general fund of information on the subject. To speak of testing an experiment by a theoretical discussion, may seem a misuse of terms, but the theories concerning falling bodies and the resistance of fluids are pretty well crystallized into laws, which may properly be used to show where experiments which seem to refute them were improperly performed, and that instead of refuting they only corroborate. It is well known that a sphere of galena & inch in diameter, and a sphere of quartz 1/2 inch in diameter, are equal falling in water ; that is, these two spheres, being placed together in a column of water at rest or in motion, will practically remain together, filling or rising together, or remaining in suspension. Mr. Krom, to show that these

Jan 1, 1879

By R. H. Smith, A. C. Polk

The physical properties of the materials are listed, together with a short explanation of how this material binds the sand grains together without materially reducing the effective permeability of the sand. The chemical can be used in wells with bottom-hole temperatures ranging from 105°F to more than 350°F A description of the equipment required and the techniques used for applying these plastics to the wells is included. Introduction Recovering oil and gas from unconsoli-dated sand formations offers one of the most troublesome of all production problems. These sands generally present no particular trouble while drilling is in progress, but after the well has been completed and a pressure differential has been established across the face of the producing zone, the formation begins to L'slough," resulting in "sanding up" of the well. The term "sanding up" means that sufficient volumes of sand have moved into the well bore or casing to cause a serious reduction or complete halt of all flow of oil, water or gas. In rare cases a well may produce only a small amount of sand and still continue to flow or pump, the sand being carried to the surface in the fluid stream. However, in such instances, the result may be a costly repair bill due to the effect of the sand on surface and pumping equipment. The difficulty of producing petroleum from sands that are loosely cemented has long been recognized by petroleum engineers but only within the last few years has any new approach to the problem been undertaken. This involves the use of plastics that are capable of bonding the individual sand grains in place without materially reducing the effective permeability of a formation. The successful application of plastics for the consolidation of poorly cemented sands is relatively recent but now it is widely used in many of the more difficult areas on the Gulf Coast of Texas and Louisiana. This relatively new use of plastics1 in the oil fields has been preceded by much laboratory and field research on the use of various chemicals2,3 for solving numerous well-completion and work-over problems. Plastics now are being used successfully to control gas-oil and water-oil ratios,4'6 in zone isolation, the repair of casing leaks, the elimination of caving in cable-tool drilling wells6'7 and in the setting of linerss and casing.9 Sand-consolidating plastics, however, are basically different from all others in that they must not form an impervious seal. Field Practices The approach to the sanding-up problem usually has been the mechanical obstruction of the movement of the sand grains.

Jan 1, 1947

By A. C. Polk, R. H. Smith

The physical properties of the materials are listed, together with a short explanation of how this material binds the sand grains together without materially reducing the effective permeability of the sand. The chemical can be used in wells with bottom-hole temperatures ranging from 105°F to more than 350°F A description of the equipment required and the techniques used for applying these plastics to the wells is included. Introduction Recovering oil and gas from unconsoli-dated sand formations offers one of the most troublesome of all production problems. These sands generally present no particular trouble while drilling is in progress, but after the well has been completed and a pressure differential has been established across the face of the producing zone, the formation begins to L'slough," resulting in "sanding up" of the well. The term "sanding up" means that sufficient volumes of sand have moved into the well bore or casing to cause a serious reduction or complete halt of all flow of oil, water or gas. In rare cases a well may produce only a small amount of sand and still continue to flow or pump, the sand being carried to the surface in the fluid stream. However, in such instances, the result may be a costly repair bill due to the effect of the sand on surface and pumping equipment. The difficulty of producing petroleum from sands that are loosely cemented has long been recognized by petroleum engineers but only within the last few years has any new approach to the problem been undertaken. This involves the use of plastics that are capable of bonding the individual sand grains in place without materially reducing the effective permeability of a formation. The successful application of plastics for the consolidation of poorly cemented sands is relatively recent but now it is widely used in many of the more difficult areas on the Gulf Coast of Texas and Louisiana. This relatively new use of plastics1 in the oil fields has been preceded by much laboratory and field research on the use of various chemicals2,3 for solving numerous well-completion and work-over problems. Plastics now are being used successfully to control gas-oil and water-oil ratios,4'6 in zone isolation, the repair of casing leaks, the elimination of caving in cable-tool drilling wells6'7 and in the setting of linerss and casing.9 Sand-consolidating plastics, however, are basically different from all others in that they must not form an impervious seal. Field Practices The approach to the sanding-up problem usually has been the mechanical obstruction of the movement of the sand grains.

Jan 1, 1947

By K. U. Snowden, J. N. Greenwood

EARLY studies by Gough and sopwith' have shown that the fatigue resistance of certain metals increased when the test was carried out in a partial vacuum; lead showed this effect to a marked degree. This communication describes surface deformation differences between high-purity lead fatigued in air and in a vacuum of approximately 5 X l0-3 mm Hg. Both air and vacuum tests were carried out by the same alternating flexure machine at a frequency of 500 cpm. Flat cantilever-bend specimens with tapered sides were cut from strip, annealed at 100°C, and chemically polished.

Jan 1, 1959

By J. J. McKetta, O. L. Culberson

A preliminary investigation was made to determine the time required to attain equilibrium within the equilibrium cell for this system. Experimental and smoothed data are presented for the solubility of ethane in water for temperatures of 100°, 160°, 220°, 280" and 340 °F at pressures to 10.000 psia. The minimum solubility phenomenon disappears at 10,000 psia within this temperature range. INTRODUCTION .is a continuation of the investigation of the behavior of hydrocarbon-water systems, the experimental data on the solubility of ethane in water have been extended to 10,000 psia. The experimental apparatus, technique, materials, and analytical methods are essentially the same as previously reported.' TIME-CONCENTRATION STUDY Prior to the initial determinations of solubility in the ethane-water system. it was desired to establish the time

Jan 1, 1950

By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By I. A. Lesk

The various materials utilized in the construction of integrated circuits, and the resultant materials interfaces, are discussed with emphasis on a materials system that is compatible with all types of integrated circuits and minimizes the number of different interfaces. Problems with interfaces may originate in the silicon, on its surface, and between other materials within the integrated-circuit package independent of the silicon. ThE difference between integrated-circuit theory and practice may generally be spelled out in terms of the difficulties in fabricating a desired structure. There are, of course, problems in forming the requisite materials, of the necessary composition and geometry, where needed. A distinct class of problem, however, is associated with interfaces— generally between different materials, but occasionally between regions of the same material. We require that each interfacial system perform its proper electrical, mechanical, and thermal function, and do so in an unchanging manner with time under the most severe operating conditions. In a practical sense, we deal in nonideal systems, such that it is generally not possible to form an interface exactly the way it was intended, even if we allow for a knowledge of the practical limitations of the fabrication system. Another way of looking at this situation is to realize that, when we form a group of interfaces under apparently the same experimental conditions, there are often differences of important consequence between them. Very high-magnification pictures, such as are obtained by an electron microscope, reveal fine structure that often differs over the area of a given sample, as well as from sample to sample. Low-magnification pictures look better, but don't eliminate the problem. The trend towards integrated circuits, and away from circuits fabricated utilizing separate components, is very strong in many areas of electronics. A typical silicon monolithic integrated circuit, still in place in the wafer on which it was fabricated, is shown in Fig. 1. The increased reliability which is being experienced through the use of integrated circuits can, to a large extent, be credited to the reduced complexity of the interface system that is present in the electronic system. A glance at Fig. 1, however, with all of its epitaxial and diffused p-n junctions, and interconnect system, shows that interfaces have been far from eliminated. Fig. 2, depicting a schematic cross-sectional view of a (partial) typical integrated circuit, illustrates in detail the numerous interfaces that occur in this type of structure. Besides the individual circuit elements, there are interfaces for isolation, and, Fig. 3, even a crossover requires a series of interfaces. What has been accomplished, however, irrespective of whether or not the total number of interfaces in the circuit is increased or decreased, is that the variety of interfaces is very much reduced. This is because there are fewer materials involved. Since the expense incurred in an R & D program to improve reliability is pretty much directly proportional to the variety of interfaces involved, it is economically advisable to work with integrated circuits for highest reliability. That is not to say that circuits built using standard components could not be made as reliable as integrated circuits, but that the expense involved because of the more complex over-all interface system would be much greater. Although electronic performance utilizing integrated circuits with all silicon elements (i.e., transistors, diodes, resistors, capacitors) is adequate for many applications, there are numerous instances where thin-film passive elements must

Jan 1, 1965

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O'Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

By B. Prof. Silliman

THE occurrence of diamonds of some size in the gold-fields of California is by no means uncommon, and was noticed by me in a communication, to the California Academy of Science in 1867, when specimens of this gem, from at least five different localities, were exhibited. I then suggested that a more attentive examination of the heavy sands left in the sluices of hydraulic washings would in all probability detect diamonds, mingled with other rare species not commonly believed to have occurred in these sands. Mr. George A. Treadwell, of San Francisco, has lately sent me a small package of these sands, collected by him from the sluices of the "Spring Valley Gravel Mining Claim," Cherokee, Butte County, California. A microscopic examination shows these sands to abound in beautiful colorless zircons (hyacinths), of the form well known in the hyacinths of Expailly (France), associated with crystals of topaz, quartz in fragments, rounded grains 'of chromic and titanic iron, and

Jan 1, 1873