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By A. F. van Everdingen

The pressure drop in a well per unit rate of flow is conrolled by the resistance of the formation, the viscosity of the fluid. and the additional resistance concentrated around the well bore resulting from the drilling and completion technique employed and, perhaps, from the production practices used. The pressure drop caused by this additional resistance is defined in this paper as the skin effect. denoted by the symbol S. This skin effect considerably detracts from a well's capacity to produce. Methods are given to determine quantitatively (a) the value of S, (b) the final build-up pressure, and (c) the product of average permeability times the thickness of the producing formation. INTRODUCTION Equations which relate the pressure in a well producing from a homogeneous formation with pressures existing at various distances around the well are generally used within the industry. The relation ii quite simple when the fluid flowing is assumed to be incompressible. It becomes somewhat more complicated when the flowing fluid is considered compressible so that the duration of the flow can he considered. In each case the major portion of the pressure drop occurs close to the well bore. However analyses of pressure build-up curves indicate that the pressure drop in the vicinity of the well bore is greater than that computed from these equations using the known, physical characteristics of the formation and the fluids. In order to explain there excessive drops it is necessary to assume that permeability of the formation at and near the well bore is substantially reduced as a result of drilling. completion and, perhaps. production practice. This possibility has been recognized in the literature. A method to compute the pressure drop due to a reduction of the permeability of the formation near the well bore. which is designated as the skin effect. S, is given in the following paragraphs. To start, equations normally used to describe flow in the vicinity of a well are given without considering this effect. These equations then are modified to include the effect of a skin on the pressure behavior. Finally a method is given to estimate the effect of the skin on the pressure and production behavior of a well. PRESSURE EQUATIONS Incompressible Fluid Flow If p is defined as the flowing pressure in a well of radius the pressure at distance r from the well has been shown to be:" The total pressure drop between the drainage boundary, and the well bore is given by These equations are valid only if the flow towards the well occurs in a horizontal homogeneous medium and the fluids are incompressible. The assumptions imply that all fluid taken from the well enters the system at r a condition rarely encountered in practice. Compressible Fluid Flow, Steady State A more realistic equation is obtained if it is assumed that the compressibility, c, of the flowing fluids is small and has a constant value over the pressure range encountered. After the well has been producing for some time so that its rate has become constant and steady state is reached, the pressures throughout the drainage area are falling by the same amount per unit of time, and the pressure differences between a point in the drainage area and the well are constant. When these conditions are met. the rate of production, q, from a well is equal to where dp/dt is the pressure drop per unit time. The fluid flowing at a distance from the center of the well is equal to From the last equation and from Darcy's law it can be shown that The equation holds for a depletion-type reservoir of radius drained by a well located in its center, provided the compressibility of the fluid per unit pressure drop is small and constant, and no fluid moves across the boundary Compressible Fluid Flow — Nonsteady State Table 111 of reference (5) shows the relationship between the pressure at the well bore and the reduced time, The pressure-drop function, p represents the drop below the original reservoir pressure, p caused by unit rate of production for several values of R, the ratio of drainage boundary radius to well radius, r In most reservoirs the values of approach infinity. and under these conditions the values of p shown in Table I of reference (5) can be used where p then signifies the difference between the pressure in the well and the prevailing reservoir pressure per unit rate of flow. The total pressure drop below prevailing reservoir pressure amounts to where the factor converts the cumulative pressure drop per unit rate of production to cumulative pressure drop for actual rate. q. For values of T > 100 the P function may be written (equation VI-15 of reference 5) as Using the time conversion the difference in pressure between reservoir and well becomes If values for the physical constants of the formation and the fluids are inserted, it is found that T exceeds 100 after a few seconds of production (or closed-in time), so that the approximation becomes valid almost at once. A simple relation between the pressure in the well and in the reservoir can also be derived by considering the well as a point source"" '" instead of a unit circle source, that is, by using Lord Kelvin's solution instead of the unit circle source

Jan 1, 1953

Discussion of the paper of F. C. NEWTON, presented at the New York meeting, Feb-ruary, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 473 to 477. H. 0. HOFMAN, Boston, Mass.-The results of these large-scale experiments, which were carried on at Perth Amboy, show that there are many differences between theoretical conceptions and their applications to work on a large scale. The author has given reasons why the results of bringing a desilverizing kettle to the high melting point of the zinc-silver alloy, Zn3Ag2, melting at 665° C., are not satisfactory. In all probability the alloy is dissolved in the lead; it may also be decomposed by the lead; the practical result is that this high temperature does not work. It remains now for the laboratory man to carry on systematic experiments

Jan 5, 1915

By Kent E. McElhattan

Selecting efficient machinery for an underground mining operation is a highly skilled art that still depends largely on human judgment and experience. In a coal mine, for example, there is no better way to predict the results of operating with a cutting machine or a continuous miner than to go underground with a sharp-pointed miner's pick. The trained eye can detect the depth of point penetration, cleavage planes, roof and floor strata, and many other conditions impossible to determine in a laboratory. Even so, however, an entirely new set of conditions may lie unexposed just a few feet behind the solid face. The candid truth of the matter is that practically nothing is known of the phenomenon of extracting a mineral from a solid. Consequently, the selection of mineral extraction machinery and systems must be based on results obtained elsewhere under apparently similar conditions. A recent study of the problem of equipment and system analysis was conducted in the coal mining regions of West Virginia. This state was chosen for study because it afforded representative sampling. The 172 coal mines investigated ecompassed seam heights ranging from less than 30 in. to over 84 in. and covered virtually all known coal mining conditions except two. The exceptions are the extreme pitch of coal seams in the western United States and British Columbia and the "bumps" encountered in the Rocky Mountains. Both of these extreme conditions are worthy of individual study.

Jan 7, 1969

By E. A. Wieselmann

This chapter presents a successful approach for achieving mine entry stability at the Cane Creek potash mine by the utilization of closure measurements. The mine is located in southeastern Utah (Fig. l). Mining is being conducted at depths in excess of 3000 ft under structurally complex geologic conditions typical of the Paradox salt basin. The closure measurement systems described have definite application for determining relative entry stability in other nonelastic rocks which are similar in behavior to potash. Similar types of closure measurements have been taken in various underground openings throughout the United States, Canada, arid Europe. Application of this closure data has previously met with varying degrees of success as a tool for design of under- ground openings in both elastic and nonelastic media.1-32 Closure measurements can be made easily and economically and they provide a practical solutiori to a practical problem. They are in-situ measurements which do not necessarily require laboratory correlation. Simple closure measurements have special significance in potash because "steady-state" ' closure rate, or creep, of the entries is measured. These closure rates can be utilized because nonelastic media such as potash will never achieve absolute stability around a mine entry. The potash will tend to creep or deform until all entries are closed and the overburden stress is redistributed over what was previously the mine area. The time for this ultimate effect to occur is dependent on a number of mining and geologic variables. Percentage of mine extraction, mining

Jan 1, 1972

By A. F. Lucas

The rock-salt deposit of Petite Anse, in Louisiana, has been known for many years. A description of it, with an account of the method pursued in its exploitation, was contributed in 1888 to the Transactions of the Institute* by Mr. Richard A. Pomeroy. But this locality does not by any means comprise the whole of the resources of the State in rock-salt. A few months ago the writer published a general account + - of all the Louisiana localities now known, together with particulars concerning their technical and commercial development. In view of the fact that active enterprises in this line have increased in number, and promise to constitute an important, if not controlling, factor in the supply of salt for the immense demand of the United States (including, as it does, the consumption of this mineral as a raw material in chemical manufactures), the present paper has been prepared. While it necessarily contains much of the substance of the article above mentioned, it is accompanied with illustrations and details not heretofore published. Moreover, the former article is out of print, the publishers having no copies left of the number of their journal in which it appeared, and the writer is therefore warranted in the belief that a paper placing the essential facts on record in a form more permanently accessible to mining engineers will be acceptable to the members of the Institute.

Jan 1, 1900

SEC. 1. The membership of the 'Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6, Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1932

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1939

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1941

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1936

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1944

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1934

By Orson Cutler Shepard

The term "electrocapillary amalgamation" is used in this paper to designate amalgamation processes that depend upon electrocapillary phenomenon; i.e., the action of an electric current upon the surface tension of mercury at the contact with aqueous solutions. Electro-capillary amalgamation is selected as a name for these processes because the electrocapillary phenomenon has been found to be the effective agent in the use of sodium amalgam, as well as in the various processes using an electric current from a source outside of the amalgam. Amalgamation processes that depend upon supplying an electric current to the amalgam from an outside source, such as batteries and generators, have previously been called electrical amalgamation processes. There has been a tremendous amount of experimental work done on amalgamation processes involving the use of an electric current, as shown by the large number of patents issued on these processes: the earliest in 1885 and the latest in 1934l. Regardless of all the experimental work, the fundamental principles causing the operation of electrocapillary amalgamation processes have not been described. The explanation usually given is that an electric current keeps the amalgam bright and clean. Patent No. 328532 states: It is well known that when amalgam plates are used for collecting gold and silver from their ores the surfaces of these plates are liable to become tarnished or sickened by certain substances contained in the ores or in the current of water which is employed to carry the ore over the plates, and that in this condition they are unfitted for amalgamating the particles of gold and silver. To prevent this and to keep the surfaces of the amalgamation plates always bright and in a better condition for catching and amalgamating the particles of gold and silver I employ electricity in the following manner: . . . A similar explanation is given 49 years later, in patent No. 1953364: The sodium (Na) ions lose their charge at the cathode becoming sodium atoms, which do not react with the electrolyte, but follow the grounded electrical current through the mercury body producing in their passage sodium amalgam and liberate themselves in the amalgamation compartment when brought in contact with the fed

Jan 1, 1939

By Orson Cutler Shepard

The term "electrocapillary amalgamation" is used in this paper to designate amalgamation processes that depend upon electrocapillary phenomenon; i.e., the action of an electric current upon the surface tension of mercury at the contact with aqueous solutions. Electro-capillary amalgamation is selected as a name for these processes because the electrocapillary phenomenon has been found to be the effective agent in the use of sodium amalgam, as well as in the various processes using an electric current from a source outside of the amalgam. Amalgamation processes that depend upon supplying an electric current to the amalgam from an outside source, such as batteries and generators, have previously been called electrical amalgamation processes. There has been a tremendous amount of experimental work done on amalgamation processes involving the use of an electric current, as shown by the large number of patents issued on these processes: the earliest in 1885 and the latest in 1934l. Regardless of all the experimental work, the fundamental principles causing the operation of electrocapillary amalgamation processes have not been described. The explanation usually given is that an electric current keeps the amalgam bright and clean. Patent No. 328532 states: It is well known that when amalgam plates are used for collecting gold and silver from their ores the surfaces of these plates are liable to become tarnished or sickened by certain substances contained in the ores or in the current of water which is employed to carry the ore over the plates, and that in this condition they are unfitted for amalgamating the particles of gold and silver. To prevent this and to keep the surfaces of the amalgamation plates always bright and in a better condition for catching and amalgamating the particles of gold and silver I employ electricity in the following manner: . . . A similar explanation is given 49 years later, in patent No. 1953364: The sodium (Na) ions lose their charge at the cathode becoming sodium atoms, which do not react with the electrolyte, but follow the grounded electrical current through the mercury body producing in their passage sodium amalgam and liberate themselves in the amalgamation compartment when brought in contact with the fed

Jan 1, 1939

By Benjamin F. Merembeck

A mutispectral scanner (MSS) obtains remotely sensed data of the earth's surface in vector form, one vector element for each spectral sensing band of the MSS. Data generated by either airborne or orbiting MSS systems are organized in a lattice of scan lines and elements within scan lines. Each element, called a pixel, is represented by an observational vector and corresponds to a relatively small specific area on the ground. The total observations for a sensed scene frequently are in the millions and are composed of a number of populations, each representing a different land form category. Based on samples from the populations, the mean vectors, or spectral signatures, and the covariance matrices for the categories may be estimated. From these, an among category covariance matrix and a combined within category covariance matrix can be found. The total among category variance is the trace of the among category covariance matrix. Canonical analysis finds a linear transformation matrix such that the first transform variable accounts for the maximum possible part of the total among category variance. Similarly, the second transform variable, orthogonal to the first, accounts for the maximum possible part of the remainder of the total variance, and so on. Such transformation often results in over 95 percent of the total variance accounted for in the first three canonical variables, even though the initial number of spectral bands exceeded twenty. Transformation of bulk data into three canonical variates allows color map products to be developed by assigning each variable to a different basic color. Such color products are believed to be more useful for photo-interpretation than color products resulting from any combinations of three of the initial spectral bands.

Jan 1, 1977

By R. S. Barneyback

Not much more is known about concrete today than was known to the Romans. For all the research only better tools have resulted to measure the quality of the materials that go into it." In this paper "some of the materials for lightweight concrete and their characteristics are considered and effort is made to indicate their effect on the end result — a structure of lightweight concrete." Lightweight concrete had noble beginnings. It is believed that the first specification for lightweight concrete was written by the Roman Emperor Hadrian in the early years of his reign, 117-138 AD. Hadrian, was an engineer by trade and an Emperor by adoption. He took considerable interest in the structures sponsored during his reign, even to the point of working out the structural details and preparing working drawings for some of the more prominent works in the vicinity of Rome. In order to reduce the dead weight of the 140 ft diam dome of the Pantheon he specified that the lightweight structural concrete members supporting this concrete and tile composite dome were to be fabricated from a concrete containing pumice and scoria. Still standing after 18 centuries of abuse, this structure has been described as the master effort of a great structural genius, the ultimate achievement of Roman engineering skill.' The Romans were the first to employ many concrete techniques we think of as modem innovations. Some unnamed superintendent noted that when a carefully measured amount of pigs blood was measured into each batch of concrete during mixing, the concrete was more durable and exhibited much better resistance to freezing and thawing climates. He no doubt, attributed this success to the appeasement of one of the gods who in return provided protection for the building containing this sacrificial offering in its walls. It is known today that the blood-entrained air in the concrete tends to make mixtures more workable, resistant to moisture penetration and more resistant to frost damage.

Jan 1, 1964

By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

Electrocarbonization of coal will produce cheap fuel for electric power plants. The complete electrification of industry and domestic power consumption of gas generated as fuel in situ is a worthwhile goal for the coal industry. Production of synthetic oils, gasoline, and coal chemicals from coal gas will create additional new markets for the coal industry. RANKING high in the nation's wealth of natural resources, readily available liquid and gaseous hydrocarbons are nevertheless falling steadily in supply, while industrial requirements for hydrocarbon compounds are greater today than during the peak period of World War 11. Theoretically, several processes will increase the future supply of liquid and gaseous fuels, but the practical application of these methods depends on two controlling factors: 1—that enough carbon-bearing material be available to warrant industrial exploitation, and 2—that the given process be physically, chemically, and economically applicable. With regard to the first factor, the Western Hemisphere is fortunately well supplied, see Table I. Table I not only shows the extensive occurrence of many fuel sources, but also the wide discrepancy among quantities of fuel substances in various materials. Great quantities of potentially available fuel have not been recovered. Many coal seams and other hydrocarbon-bearing deposits are so situated that production is uneconomical by present-day mining or oilwell pumping methods, and even in many exploitable deposits where the most efficient production methods are used a large proportion of material is never recovered. Industrial production of hydrocarbon liquids and gases must be better balanced, and processes must be developed which will convert coals, oil sand, and oil shales into fabricated commodities. Among the techniques employed by scientists and engineers to secure fuel masses not economically available at present are several processes of underground gasification. These are all concerned with converting raw materials into gaseous products by thermal treatment of source substances while they are still in the ground and therefore require that a subsurface heat (fire) zone be induced to affect pervasively the buried raw fuel deposit. This is possible only where sufficiently high temperature exists and where the fuel material is satisfactorily opened or channelized. Also, to compete successfully with common mining or oilfield practices, a given method must be controllable and must not involve greater operational expense than regular methods. Preferably, it should be less expensive. Since the close of World War 11, England has continued field studies of underground gasification methods. Experiments have also been conducted in Sweden, Estonia, France, Belgium, Italy, and Germany. The U. S. Government has sponsored field studies at Gorgas, Ala., and because gasification in situ is vitally important to establishment of the nation's fuel resources, the mining engineering department at the Missouri School of Mines has been actively interested in developing the process of underground electrocarbonization. Research was conceived by Erich Sarapuu, and preliminary experiments in treating bituminous coal were begun at the school in September 1947. The work consisted of laboratory experimentation until June 1948, at which time, through a cooperative agreement with the Sinclair Coal Co. of Missouri, pilot plant studies were instituted at the Tiger mine of the Hume-Sinclair Coal Co. near Hume, Mo., to test the encouraging laboratory findings. This comprehensive field program was pursued continuously until the beginning of 1952."'" The broad term underground electrocarbonization describes a unique gasification process that releases by electricity the desired economic constituents from a raw carbon-bearing material, converting the substance of such deposits into deliverable form and greatly reducing the cost-of-mining factor. Underground electrocarbonization is not subject to the major limitations of many other underground gasifi-

Jan 1, 1955

By Edward W. Parker

This plant was built in 1907 at the Bankhead mines to manufacture briquettes by the Zwoyer process under license from the Zwoyer Fuel Go., of New York, N. Y. The building was constructed to contain two units, each of a capacity of 10 tons per hr.; one unit was installed at the time the building was constructed, and the second unit is now being built. The coal used is an anthracite, which is more friable than that of Pennsylvania, and, as a consequepce, a larger percentage of dust or waste is produced, which was formerly thrown upon the slack-pile as waste, but is now passed to the " dust-bin " in the breaker, from which it is conveyed to the briquette-plant. An average analysis of the coal, published by Lewis Stockett and 13. R. Warden,' is as follows: Per Cent. Moisture,.........0.50 Volatile,..8.00 Fixed carbon,... 83..50 Ash,.......8.00 Total,.100.00 Sulphur,.........0.40 per cent. Specific gravity,...... 1.40 Color of ash,.white Heat value,.......14,000 B.t.u. The plant is run under two 12-hr. shifts, the force consisting of 1 superintendent for both shifts, 1 engineer for each shift, 1 briquetter for each shift, 1 helper for each shift, 1 laborer cleaning up for each shift. In the pitch-melting house, 2 men are on duty for one shift. The steam for the engine is furnished from a central boiler-plant, which also supplies steam for the breaker, the electric light and power-plant, machinery-shop, and boiler-shop. During March, April, May, and half of June, in 1907, the

Jan 1, 1909

By Orson Shepard

THE term "electrocapillary amalgamation" is used in this paper to designate amalgamation processes that depend upon electrocapillary phenomenon; i.e., the action of an electric current upon the surface tension of mercury at the contact with aqueous solutions. Electro-capillary amalgamation is selected as a name for these processes because the electrocapillary phenomenon has been found to be the effective agent in the use of sodium amalgam, as well as in the various processes using an electric current from a source outside of the amalgam. Amalgamation processes that depend upon supplying an electric current to the amalgam from an outside source, such as batteries and generators, have previously been called electrical amalgamation processes. There has been a tremendous amount of experimental work done on amalgamation processes involving the use of an electric current, as shown by the large number of patents issued on these processes: the earliest in 1885 and the latest in 19341. Regardless of all the experimental work, the fundamental principles causing the operation of electrocapillary amalgamation processes have not been described. The explanation usually given is that an electric current keeps the amalgam bright and clean. Patent No. 328532 states: It is well known that when amalgam plates are used for collecting gold and silver from their ores the surfaces of these plates are liable to become tarnished or sickened by certain substances contained in the ores or in the current of water which is employed to carry the ore over the plates, and that in this condition they are unfitted for amalgamating the particles of gold and silver. To prevent this and to keep the surfaces of the amalgamation plates always bright and in a better condition for catching and amalgamating the particles of gold and silver I employ electricity in the following manner:. . . A similar explanation is given 49 years later, in patent No. 1953364: The sodium (Na) ions lose their charge at the cathode becoming sodium atoms, which do not react with the electrolyte, but follow the grounded electrical current through the mercury body producing in their passage sodium amalgam and liberate themselves in the amalgamation compartment when brought in contact with the fed

Jan 1, 1936

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By Donald A. Brobst

The minerals barite (BaSO4-barium sulfate) and witherite (BaCO3-barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1980 consumed at least 90% of the world's production of 8.8 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The remaining 10% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity filling, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favorable for the discovery of new deposits of commercial value. Witherite is much less common and abundant than barite, although it is more desirable in many ways as a raw material for the production of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir conditions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemically, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite homogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber industry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and linoleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other substances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weigh down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1983