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By N. M. Levine

WHETHER the United States and its allies can W meet the challenge of a war brought by the Communists will depend largely on who wins the battle of steel production. At the present stage of the world situation, the United States and the other members of the Western family of nations have the lead on iron curtain countries. But we have no sure way of knowing what is happening at Magnetogorsk and other Russian iron and steel producing centers. We must also face the possibility that we may have to meet the challenge alone. The fortunes of war and world politics can strip us of friends and co-fighters quickly. The destruction of Hiroshima and Nagasaki are indicative of what the world can expect if war-madness ever grasps the earth again. Our domestic supply of high grade open-pit and underground iron ore is dwindling because of the drain of three wars and higher than ever civilian consumption. The production of iron ore and its eventual use in blast furnaces are the critical problems of an armed democracy today. The world crisis has led to efforts towards beneficiation for increasing ore supplies. The huge reserves represented by the magnetic taconites at the eastern end of the Mesabi, once in production, should provide us with a substantial portion of our native ore for many years. The estimated 10 to 20 million tons of concentrates annually can be increased in an emergency. If we had a certainty of peace for the next 50 to 100 years, the situation would be a stable, hopeful one, aided by importations of high grade ore from sources such as Canada and Venezuela. The hard truth is that we have little surety of peace tomorrow morning. Let us assume 'the U. S. could build sufficient processing plants for increasing production of magnetic taconites under the pressure of national emergency. We must also recognize the power of atomic warfare to contaminate an area as large as the Eastern Mesabi. Thus, it becomes imperative to seek some means of protecting our ability to produce the steel we may one day need to survive. The nonmagnetic taconites, completely dwarfing the magnetic taconites areawise as well as tonnage-wise, might provide us with this insurance. Present indications are that they will be considerably more expensive to treat, but in a desperate situation we might be very grateful for ores yielding 40 to 50 pct Fe recoveries at grades of 53 to 58 pct Fe carrying low phosphorus. The University of Wisconsin, because of the difficult iron ore situation in the state, has been working on the nonmagnetic taconite problem for the past three years in the hope of making a contribution toward its eventual solution. In Wisconsin, the Western Gogebic Range has been the state's most effective iron producing area. Today however, only two mines are in operation, both underground and approaching depths of more than 3000 ft. The range, however, does have a large supply of nonmagnetic taconites and presents a promising field for study. While the Gogebic offers one large source of nonmagnetic taconites, Michigan and Minnesota have even greater supplies of such material. Alabama, the northeastern states and the West all have low grade iron ore sources which might be utilized under extreme conditions. The Gogebic Range located in northeastern Wisconsin and northwestern Michigan has a total length of about 70 miles, about 45 of which are in Wisconsin. The iron formation averages 500 to 600 ft in width, dips 70' to the north and strikes at approximately N 63° E. The formation is sedimentary and consists of six distinct members characterized by alternating divisions of ferruginous chert and ferruginous slate. The footwall is generally quartzitic and the hanging wall of a sideritic slatey character. The iron minerals are mainly hematites with some magnetites, goethites, limonites and small amounts of siderite. In the area studied, very small amounts of iron silicates were observed. The magnetites occurred mostly in the Anvil-Pabst and Pence members, mixed with hematites and representing roughly about 10 to 20 pct of the total iron in the formation, thereby characterizing it as nonmagnetic. The gangue is of various forms of silica such as chert, opal and flint. Complete liberation of iron and gangue minerals is rare. There is always some iron present in the chert ranging from jasper-like solutions to fairly coarse iron oxide specks. Likewise, one always finds finely dispersed silica within the iron minerals. In late 1943 the Bureau of Mines carried out a trenching and sampling program in the two mile stretch between Iron Belt and Pence in Iron County, Wis. Preliminary work was based on samples from one of the four trenches cut by the Bureau of Mines. More detailed work following the preliminary analysis was then undertaken on samples composited from all the trenches, thereby giving a wider and more representative coverage of the area. A study of the

Jan 1, 1952

By F. W. Bryan, D. H. Lynch

Introduction This paper is a general description of current central Florida phosphate mining, beneficiation, and product transportation. It is directed and believed to be of interest to engineers not familiar with this industry. Deposit: The phosphate deposits of central Florida are generally located in a five county area which includes Polk, Hillsborough, Hardee, Manatee, and DeSota counties. Geologically, the deposit is of marine origin and is identified as the Bone Valley formation. This formation is Pliocene to Recent in geological age and overlies a Miocene limestone formation known as the Hawthorn. The Bone Valley formation sediments are regionally characterized by equal proportions of apatite, quartz, and clay. The clay is predominantly of the mont-morillonite family. On a local scale, however, the proportions of these three major constituents vary considerably. The phosphate occurs as the apatite mineral (Ca 10F2(PO4)(6) and with the clay and sand, the minable ore is commonly referred to as matrix. This matrix is overlain by unconsolidated overburden of sand and sandy clays, ranging in depth from 10 to 45 ft. The matrix usually occurs in fairly horizontal continuous beds from 3 to 25 ft in thickness. The bedded limestone formation lies directly below the matrix and is generally well defined. The phosphate particles range from 3/4 in. to 200 mesh (Tyler) in size. The phosphate particles coarser than 14 mesh are called pebble phosphate and those less than 14 mesh are termed flotation feed which, when beneficiated, subsequently become concentrates. Through mining and beneficiation, phosphate quality is measured in BPL percent which stands for bone phosphate of lime units. In subsequent chemical manufacturing, the quality is indicated by P205 content. The deposit is economically characterized by various ratios such as tons of product per acre and cubic yards handled per ton of product. Magnesium, iron, and aluminum content are also considered in evaluating ore reserves. These elements are often critical to the chemical fertilizer processes. Presently, an ore body is considered economically minable if it meets the criteria shown in [Table 1]. These, of course, are general guidelines and specific costs and returns on investment must be considered in each case for acquiring reserves. On a new grass-root venture, a 20-30 year life is generally expected with a mineral recovery of 80%. History and Uses Phosphate mining in central Florida began around the turn of the century. However, in the early days, only pebble phosphate was produced until about 1930 when technology was available to beneficiate the -14 + 150 mesh particles. The -150 or -200 mesh material was discarded as it is today. The basic processes for beneficiation are washing, scrubbing, desliming, sizing, and flotation. These basic unit processes are essentially the same today although many improvements have been developed since the early days. Phosphate is used primarily in the production of high analysis fertilizer chemicals, typical of which are triple superphosphate, monoammonium phosphate (MAP), and diammonium phosphate (DAP). Phosphate is also used in the production of food preservatives, dyes for cloths, vitamin and mineral capsules, steel hardeners, gasoline and oil additives, toothpaste, shaving creams and soaps, bone china dishes, plastics, optical glass, photographic films, light filaments, water softeners, insecticides, soft drinks, road fill, and livestock feed supplements. Florida produces over 80% of the nation's marketable phosphate rock and one-third of the world production, according to the US Bureau of Mines. This amounted to approximately 35 million tons in 1975. Exports of Florida phosphate rock were to such countries as Canada, Japan, West Germany, Italy, and India, with Canada and Japan being the major users. Almost 95 o of all outbound cargo shipped through the port of Tampa is phosphate rock or related products. Beneficiation Following is a description of Agrico's new Fort Green beneficiation plant which is typical of the newer large capacity plants being built in the field. Agrico's Fort Green mine was completed in 1975 and is located in the southwest corner of Polk County and is directly adjacent to Manatee, Hillsborough, and Hardee Counties. With some minor differences, Fort Green is typical of a modern central Florida plant. The rated capacity is 3,000,000 plus tons of product per year and this varies according to the richness of the ore being handled. A simplified flowsheet is presented in [Figs.1 and 2]. This plant is served by three draglines of the 40-cu-yd class. The phosphate beneficiation is usually divided into three major functional steps: (1) washing and screening to produce a pebble product and flotation feed, (2) feed preparation and (3) flotation to produce concentrates. The typical plant is similarly divided into these three functional areas. Washer: Briefly, the slurried matrix is pumped from two draglines simultaneously at a combined rate of about 20,000 gpm at 2000 tph (solids) to rotary trommel screens sized to make a 7/8-in. separation. ([See Fig. 1]-) The trommel oversize is sent to hammermills where it is crushed and returned to the trommel screens, or pumped to tailings if minor impurities (Fe203, A1203, MgO) are too high. The trommel undersize is pumped to 14 mesh stationary (static) flat screens. The flat screen over¬size is subjected to three stages of 14 mesh vibrating screening and two stages of log washing in order to produce a final pebble product. The pebble product (+ 14 mesh material) is conveyed by belt conveyor to a large on-ground storage pile. Pebble product is reclaimed through a tunnel and loading system below

Jan 1, 1980

Jan 1, 1911

By R. P. Rothwell

Jan 1, 1885

By Paul Averitt

require both time and money. Any attempt to secure a quick answer will yield a figure that very likely cannot be substantiated, and certainly will not yield information in the detailed form now desired. It will be about 10 years before a completely new estimate can be prepared for the coal reserves of the United States at our present rate of progress, though of course, much information will be available in the interim. We would like to present such information as we obtain in the form most acceptable to the industry, and to that end we are working closely with coal resource committees of the AIME, the National Bituminous Coal Advisory Council, and the Bureau of Mines. DISCUSSION G. H. Cady*—Mr. Averitt's description of the nature of the coal resources investigations of the United States Geological Survey and the progress of this work is very timely in view of the general interest in the subject of coal resources. The Federal Survey is obviously taking the "long view" with respect to the appraisal of the coal resources as part of the preparation of the general geological map of the country and the attendant determination of the quantity of all mineral and fuel resources. It is apparently for regional surveys of the conventional type that the detailed procedures employed by the Federal Survey are applicable. Even if so it is somewhat unexpected to find the same criteria for evaluation will be applied to the country as a whole. The work on coal resources appraisal has been proceeding at various rates in a number of coal producing states for various periods. Undoubtedly since there has been no common practice in the method of appraisal the states each have worked independently and independently of the Federal Survey, and each has adopted certain practices to meet local conditions. I do not know how much consideration has been given by the U. S. Geological Survey to these practices. It seems probable that such consideration might result in important modifications of the standards which apparently have been set up by the Federal group in line with local requirements. It is the practice in some state surveys to present the facts in regard to the occurrence and distribution of coal beds and their variations in thickness down to thicknesses of 1 to 1 1/2 ft in relatively narrow stages up to maximum thickness. It is then possible for any one using such figures to compile quantitative estimates of workable coal at various minimum thickness limits. This is a desirable objective where surveys are detailed and information correspondingIy good. However, vast quantities of coal lie in beds that are relatively thin about which little information is available and the quantity of such coal might affect the final appraisal to the extent of several thousand million, depending upon the minimum limitation observed. Thus in the case of Illinois a difference of 1 ft in average thickness of coal in the coal field would make a difference of approximately 35 billion tons in the estimated quantity present. One is dealing with a very large area and small differences in thicknesses are very irnportant in the overall picture. The estimate of 10 years to accomplish the sort of detailed appraisal outlined by Mr. Averitt is viewed somewhat skeptically and certainly would require many more trained geologists than seem to be available. The requisite detailed mapping and study are very time consuming not only because of the geological field work required, which is difficult in certain seasons, but also in order to assemble data from company and personal files, and to study drill records and cores, and to sample and analyze the coal. Unless the staff of geologists could be increased in the order of several hundred per cent the prospects are that the appraisal of the type suggested will require many decades not just one. The permanent value of such appraisal, however, is not questioned and it should be expedited as rapidly as means allow. Satisfactory appraisal is not easily achieved and will vary from time to time. The main function of a geological survey is to collect and present the facts that will make possible appraisal in terms of existing conditions by individuals, particularly engineers, qualified by training and expcrience for making such estimates. Thickness and character of the coal bed, nature of the overlying and underlying strata, position, thickness, and character of "partings," relationship to other coal beds, and a variety of other factors must be assembled by the geologist in order to present a complete picture of the geological setting. The economic and engineering factors are in general outside the field of geological experience. The geologist should see to it that the pertinent geological facts are available; much more information than simply thickness and depth of the coal beds is essential to meet all the requirements of appraisal in the future as well as at present. With respect to the present demand by engineers and coal mine operators and others for a rapid re-appraisal of the available coal resources, in the light of existing practices and those in immediate prospect, the Federal procedure of systematic mapping and appraisal is scarcely in line. It will be necessary for those particularly interested in having such an estimate made to establish standards with respect to the various factors involved so that the scope of the geological work can be definitely restricted for the various coal fields. There is little use in setting up general standards since no such standards will be applicable to all fields. Thus it is folly to establish a standard minimum thickness to be generally applicable which is one-half to one-third the minimum minable thickness in some fields. The greatest difficulty in appraisal of the presently actually workable coal bed lies in the variation in the importance placed on roof, floor, structural conditions, bedded impurities. sulphur content and other factors that affect judgment relative to the value of a coal bed. It is doubtful whether any appraisal will have universal approval in view of the variable factors involved. For this reason if none other, the facts should be carefully and painstakingly assembled after the manner of a systematic geological survey such as that advocated by Mr. Averitt. Only upon the basis of sucb information can reliable estimates be made in line with selected conditions. Paul AveRitt (author's repty)— In this paper I discussed, but did not define as such, two major phases of our activities on coal, which are closely related, and which normally we in the U. S. Geological Survey see as an integrated whole. It is understandable, therefore, that Dr. Cady should assume that my remarks applied only to the current work on coal reserves with which I am directly concerned. In view of Dr. Cady's discussion, however, I think a brief summary of the two phases of U. S. Geological Survey activities on coal will be appropriate. The long-term function of the U. S. Geological Survey on coal investigations is to make detailed geologic studies, involving the preparation of detailed geologic maps showing the outcrops and correlations of coal beds, direction and dip of coal-bearing rocks, nature and thickness of overburden, location of faults and fold axes, and similar features. Such studies also yield many measured sections of coal and associated strata, which show variations in the thickness of the beds, and the intervals between coal beds. Taken as a whole, detailed geologic studies provide much useful information for mine operators and engineers. As Dr. Cady points out, this type of geologic work is arduous and time consuming, but it provides the basic data that are necessary both in the development of our coal fields, and also in the preparation of coal-reserve estimates, which are discussed in the next paragraph. The U. S.

Jan 1, 1950

By S. FROES ABRUE

No new oil fields were discovered in Brazil during 1945. Production for the year reached a total of 79.329 bbl., all coming from the four fields in the Baia basin; the Lobato-Joanes field produced 6728 bbl.; Aratu, 6717 bbl.; Candeias, 36,663 bbl. and Itaparica, 29,211 bbl. The total cumulative production from the Baia basin from 1939 to 1945 inclusive amounts to 210,000 bbl., all of which is utilized locally.

Jan 1, 1946

By Samuel Hoyt

THE hardness of annealed copper has been given in the literature and is easily obtained by any of the standard methods of hardness testing. It is not our intention to correct published values or to add to them, but to describe tests of two bars of annealed electrolytic copper in which the methods of Meyer's analysis were employed. MEYER'S ANALYSIS OF BALL INDENTATION TEST The ball indentation test is probably the most valuable hardness test we now have but, as it is carried out in the Brinell or Rockwell test, the result may be seriously in error without the operator suspecting such to be the case. This condition results from the isolated and uncontrolled nature of the measurement. The accuracy depends on the accuracy of the equipment and the care and skill used in the operations; there is nothing in the impression diameter, which is all that is measured, to indicate the presence of error. Meyer's analysis supplies a control of the measurements that goes far toward eliminating unsuspected errors. The principles of this work maybe obtained from elsewhere.1 As this subject has not received the attention of this Institute, it may be well to summarize the more important points as follows.

Jan 2, 1926

By Edwin Dudley Martin

DURING the past twelve years the iron and steel industry has made a major advance through the development of the continuous wide strip rolling mill. So far-reaching have been the results that not only has a better product been sold at a lower price but this improvement in quality has permitted manufacturers of products using steel to make important savings in the cost of fabrication. The net result has been a better product at lower cost to the consumer without reduction in either employment or of wages paid within the industry. That is why the iron and steel industry is proud of its attainment. Being a basic industry of strategic importance, such an advance in technology has had its effects on our internal economy, our standard of living, and our industrial power as a nation in both peace and wartime.

Jan 1, 1939

By D. Hawington

HEALTH and safety in the mining and allied industries of the United States have unquestionably been progressing, particularly during the past three or four years, even though the progress has been anything but great in some branches of these industries. Statistical data to support this statement are readily available as to safety, but similar health data are unfortunately not available. In coal mining the rate of occurrence of fatal accidents per million tons of coal produced for the ten-year period 1911.20 inclusive was 4.27; this rate was 3.84 in 1930, .3.31 in 1931, 3.36 in 1932, and 2.69 (tentative) in 1933. In metal mining, the-rate of occurrence of fatal and- non-fatal injuries per .thousand 300-day workers (calculated) was 224.36 for- the same ten-year period. This fell slowly until after 1929 when it was 203.14, dropping to 170.78 in 1930, to 142.09 in 1931, to 138.46 in 1932, and to 155.13 in 1933. Here, again,-the real progress began in 1931 though the rate in 1930 was not particularly bad. For the same ten-year period, the rate of those killed and injured: in: quarrying per thousand 300-day workers (calculated)

Jan 1, 1935

By K. J. Powers

The Mine Accident, Injury, Illness and Employment Database at the Mine Safety and Health Administration's Health and Safety Analysis Center is a computerized system that stores accident, injury, illness and employment data about all coal and metal/nonmetal mines in the United States. The paper discusses the system for collecting, storing, analyzing, and reporting this information and how these data are used in the ongoing effort to increase the health and safety in this nation's mines.

Jan 1, 1983

By Willard C. Lacy

Rather than attempting to present a summary of the many and highly varied papers that have been presented at this symposium on sampling and grade control, I will attempt to extract the general philosophy of analysis and approach, and attempt to identify the trend of future developments. First, the term "sampling" is used with its broadest connotations. A sample consists of a representative portion of a larger mass, and must represent the mass not only in the grade of contained metals or minerals, but also in all other respects in terms of mineralogy and mineral quality (1, 5), deleterious materials, recoverability of economic components, physical behavior, geophysical response (I), and even archaeological and environmental aspects (7, 11). The sample must be taken from a locality and in such a manner and quantity that it is representative of the larger rock mass. This calls for complete and accurate geological control and an understanding of the nature and distribution of the contained chemical and physical elements and a record of the effectiveness of the different sampling methods. Second, value of a given mass of ore material is based upon its profitability - the difference between recoverable value and costs to achieve recovery, beneficiation and sale. There is a strong movement in mining geology control toward more complete analysis in determining cutoff grades and in grade control, as illustrated by the kriging of metallurgical recovery factors as well as grade at the Mercur Mine (8). To achieve a "profit- ability factor" as a guide for economic mining practice requires further integration of: 1) the value of contained metal or mineral, 2) percentage recovery of values, 3) dilution of ore with waste rock, 4) addition to, or loss of value as a consequence of by-product materials or deleterious components, 5) cost of producing a saleable product plus mini- mum profit to justify the effort (cutoff), and 6) cost of land restoration (7, 11). All these parameters vary with the rock type, rock structure, mineralogy, depth, geometry, mining and metallurgical methods, but they must be sampled and analyzed if sampling and grade control are to reflect profitability. A wide variety of deposits has been presented at this symposium; each deposit with its own problems and special solutions. Deposits containing high unit-value components, e.g. precious metals and diamonds, present special problems in the obtaining of accurate samples and generally require statistical analysis control methods or may disregard or modify occasional high or occasional low values, based upon experience (12 ) Grade control may be accurate for the long term but may vary for the short term. Bulk sampling is always essential. Deposits containing metals or minerals with low unit value are very sensitive to transport costs, and they are often very sensitive to small amounts of deleterious components or differences in physical or chemical behavior. Problems of sampling and grade control change with the genetic type of deposit, with the stage of deposit development and with the size of the information base. Precious metal epithermal deposits (2, 6, 8), because of rapid vertical zonation and erratic lateral distribution of values, have always been difficult to evaluate and maintain grade control and ore reserves. On the other hand, evaluation and grade control are relatively easy in bulk-low- grade deposits (4, 13). However, these deposits generally have a low margin of profit and are sensitive to mining and beneficiaton costs, price fluctuations and political costs. Industrial mineral deposits (5) often must be evaluated on the basis of their behavior, rather than by chemical analysis. Environmental impact generally increases with the scale of the operation, but certain elements or minerals have especially high impact effects (7, 11). In the exploration phase there is no production control of sampling procedures and careful geological observations are particularly essential. The greatest number of problems is related to the oxidized outcrop where the chemical environment of the ore body has changed and the contained values may have been enriched, depleted or values left unchanged (2, 6). Present evidence suggests that gold values may be very mobile under certain conditions (2, 6) and stable under others. Everything must be sampled in detail. Principal values and by-product or deleterious elements may vary dependent upon their position within the soil profile. Such factors as geomorphic position, erosion rate, vegetation, climate, etc., may affect the interpretation (1, 3). During the development phase it is equally easy to overtest, to have "paralysis by analysis," as to undertest (3, 6). Bulk samplng and testing are

Jan 1, 1985

By AIME AIME

THE difficult problem of visitors is being met by the Hudson Coal Co. at Scranton in an ingenious fashion. The Company had long made it a point to have dealers selling its coal visit the mines, whenever possible. "The excellent reaction obtained from these dealer visits brought up the question of whether it would not be possible to open one or more mines to the public, and give the consumer an opportunity of seeing for himself how anthracite is mined and prepared. Ac-

Jan 1, 1929

By Hisaaki Takata, Nobukazu Nanko, Ichiro Izawa

INTRODUCTION Tochibora Mine belonged to Kamioka Mines, which are located in Gifu Prefecture, the cen- tral part of the Japanese main island, has occupied the important position as a main source of silver, lead and zinc for the smelter of Mitsui Mining & Smelting Co., Ltd.. The annual production of crude ore goes up to about 1 mil- lion metric tons with average grades of 20g/t Ag. 0.31% Pb, and 4.18% Zn. For the last 20 years, the mine has struggled with the depressed zinc metal price in yen and the escalation of operating cost, especially la- bour cost. For instance, prices of commodities and labour cost have been raised 8 times and 14 times respectively during this period. On the other hand, total operating cost has been con- trolled to increase 4.5 times. The productivity of the mine has been increased 4 times by means of improvement of individual works and adoption of perfectly mechanized trackless mining system to reform the mining method. Some improvements are presented as follows; Today, drifting is carried out by the tunnelling crew which consists of 9 operators equipped with 5 Mobile-Jumbos, 2 LHD's and a jeep for carrying and loading ex- plosives. In order to get the high utilization of these machines, each crew manages systematically and continuously adjacent 15 faces under the direction of a forceman. As a result, we have accomplished high advance of drift. Furthermore, raising is carried out by a set of the raise-borer in case of long raises like ore- passes and also by the stage blasting method in case of short ones like slot-cuts. Generally speaking, the sublevel stoping method is considered to be one of the best methods for various respects; high productivity, low cost, easy grade control and safety. This method has been introduced in Tochibora Mine since 1950 and is now widely applied to lodes that could not be mined before by this method be- cause of the shapes of them and the conditions of their country rock. Now we are convinced to be nearly accomplished for our method. This report presents some examples of the standard sublevel stoping method and its variations which are practised at the mine. STANDARD SUBLEVEL STOPING Up to 1979 since 1950 when this method was first applied at the mine, 17 million tons of crude ore have been produced by this method, which amounted to 55% of the total production of the mine. During three decades, the productivity has been increased considerably by means of trackless mining system using large-sized machines and etc.. In other words, mining efficiency has been increased from 20 tons/man.shift to 100 tons/man.shift at large stopes. Formerly undercutting was carried out above the drawing drift by jack-legs and small scrapers and then several cone-shaped glory holes were made by stopers between the undercut level and the draw level. But now, a undercut drift is driven in parallel with the haulage drift at the same level of it. And at the undercut drift, drilling upward is carried out by a large-sized machines like the fan drill in order to extract the broken ore directly at the drawing drift connected with the haulage drift. Simplification of the work as well as utilization of large- sized machines enables to get higher productivity. But if the deposit is comparatively wider and the broken ore around the middle part of the deposit cannot be extracted, several drawing drifts are driven to the deposit and in order to minimize dead ore at the final stage of operation, the

Jan 1, 1981

By T. L. Loucks, E. T. Guerrero

Pressure drop characteristics in a system composed of two adjacent concentric regions of different permeability were studied. The differential equations for continuity of mass flow in the two regions were solved using the Laplace transformation and the necessary boundary conditions to give the pressure distribution in the composite reservoir, the resulting equation for pressure drop at the inner boundary was evaluated for a variety of composite reservoirs and compared with the results for a uniform reservoir. From this study it was found that under certain conditions the permeability in both zones, as well as the size of the inner zone, can be determined from the pressure drop curve. INTRODUCTION The theory for the pressure distribution and pressure build-up behavior of a well producing a single, slightly compressible fluid from infinite and finite homogeneous reservoirs was presented by Hornerl and Miller, Dyes and Hutchinson.2 Extensions on this original work to provide improved and extended interpretations and better agreement between theory and observed results have been made by Matthews, et a1,3 van Everdingen,4 Gladfelter, et al5 Stegemeierand Matthews,6 Hurst and Guerrero,7 and Perrine.8 More recently Lefkovits, et al,9 studied pressure build-up behavior in bounded reservoirs composed of stratified layers. Houpeurtl0 has suggested various approaches to the general problem of variable permeability and porosity but presented no analytic solutions for particular permeability variations. Albert, Jaisson and Marionll studied the finite composite reservoir and presented numerical solutions to the unsteady-state case and an analytical solution valid only for large times. They also studied the so-called pseudo-steady state for several examples of radial permeability variations. Very similar examples have been treated in the unsteady state with application to pressure build-up by Loucks in an unpublished manuscript. More recently Hurst12 has presented the complete point-sink solution (valid for all times) for the infinite composite reservoir. He applied these solutions to interference between oil fields along with an even more elegant application of his explicit solution to the material-balance equation including water influx. Mortada 13 approaches the same application by avoiding the point-source limitation but gives the solution for the aquifer region which is valid only for large times. Hopkinson, Natanson and Temple14 have treated both the finite and infinite composite reservoir obtaining the pressure distribution for the inner zone valid for large times. This paper presents a theoretical study of the pressure distribution in an infinite composite reservoir composed of two adjacent concentric regions of different permeability. The object was to determine the manner in which pressure drop at the inner boundary of a composite reservoir depends upon time, the permeability of each zone and the size of the inner zone. Expressions for the pressure distribution in both zones are developed which take into account the radius of the sink and are valid for small times as well as large times. It was felt that an understanding of the pressure drop behavior in various composite reservoirs would be of assistance in the interpretation of some pressure build-up curves which do not behave according to the theory derived for uniform systems. Often the region surrounding the wellbore is either more permeable or less permeable than the reservoir because of the various drilling and completion practices. The effects of reduced permeability due to drilling-fluid invasion and of increased permeability due to fracturing or acidizing need to be more carefully defined. Therefore, an equation for the pressure drop in a composite reservoir was developed, and the effects of both the permeability in each zone and the size of the inner zone were studied. STATEMENT AND SOLUTION OF PROBLEM BOUNDARY CONDITIONS AND ASSUMPTIONS The physical system studied was a composite

By C. R. Masson, M. L. Pearce

The nitrogen contents of seven specimens of iron and steel were determined by the three methods. Good agreement won generally observed between the results of the isotope -dilution and Kjeldahl determinations, tltzts establishing the reliability of the isotope -dilutzon technique. For some specimens, the vacuum-fusion values at 1650 °C were lower than the corresponding Kjeldahl values by up to 0.0015 pct absolute. These differences were eliminated for a specimen of "pure" iron by performing the vacuum-fusion analyses at 2100 ° to 2240 °C. The reason for this relatively high temperature required m the vaczium-fusion analyses is discussed. ThE determination of nitrogen in iron and steel has been the subject of numerous investigations and a concise review of the extensive literature in this field has recently appeared.' Two methods of analysis are most commonly employed, the vacuum -fusion and the chemical or Kjeldahl method. Except in special cases where the presence of certain alloying elements may present difficulties, both methods are generally regarded as applicable, although the vacuum-fusion method is more sensitive and is often preferred for samples of very low-nitrogen content. The method of isotope dilution, first employed for the determination of gases in metals by Kirshenbaum and Grosse,2 has recently been applied to the determination of nitrogen in iron and steel.3,4 The method is attractive in that it does not require the quantitative extraction of gas from the metal specimen. Staley and Svec3 modified the standard Kjeldahlpro-cedure by introducing, along with the steel sample, a measured amount of ammonium sulfate enriched in the isotope 15N. The nitrogen content was obtained by measuring the isotopic ratio 15N/14N in the resultant solution. The technique involved the distillation of nitrogen as ammonia from alkaline solution and subsequent oxidation of NH4+ in the distillate to gaseous nitrogen. The results for iron and steel samples of commercial origin were often in reasonable agreement with values quoted by the suppliers, although occasional marked discrepancies were observed, particularly with the results of vacuum-fusion analyses. Preliminary work in this laboratory4 on the determination of nitrogen by isotope-dilution in the gas phase yielded results for three samples which were significantly higher than the values obtained by vacuum-fusion. The present paper describes an extension of this work to a wider variety of samples. Analytical results by the Kjeldahl method are also reported. EXPERIMENTAL The technique employed for the isotope-dilution determinations was similar to that described elsewhere.4 Several minor modifications were made to the apparatus. These included the use of molybdenum instead of platinum-rhodium suspending wires when crucibles were degassed at temperatures above 1600°C. The circulatory system used previously for converting CO to CO2 was replaced by a single chamber, the walls of which were cooled directly in liquid nitrogen. Temperatures were measured with an optical pyrometer which had been recently calibrated and, as in the previous study, were minimum values obtained by sighting on the center bottom of the crucible. Temperatures obtained by sighting on the interior walls were always higher by 100' to 130°C with the design of crucible employed. Flat-bottomed crucibles exhibited an even larger temperature difference. To check the efficiency with which crucibles were degassed in the isotope-dilution apparatus, several experiments were done in the vacuum-fusion apparatus, suitably modified4 for isotope-dilution studies. Faster pumping speeds and higher degassing temperatures were possible, the latter due to the use of a generator with a higher power output (10 Kva at 398 kc per sec). In these experiments the combustion of CO was omitted and a correction4 was made for the contribution of CO to the ion current at m/e 28, used in determining the isotopic ratio R = l5NP4N. This correction did not seriously influence the re-

Jan 1, 1962

By T. J. Whalen, M. Humenik

The liquid surface tension of copper-nickel ad copper-nickel-titanium-carbon alloys and the wettability of titanium caybyde by these alloys have been measuhed. It was found that the surface tensions of the binary copper-nickel alloys Lie on a smooth curve between the end members, copper and nickel. The addition of small amounts of titanium and carbon has nO effect on the surface tensions of copper-nickel alloys. Small additions of nickel to copper significantly reduce the contact angle of Ike alloy with titanium carbide. From a Gibbs treatment, nickel is shown to be adsorbed at the titanium carbide-alloy interface. X HE microstructure of two-phase materials has been shown to be influenced largely by the interfacial energies between the phases present.' , In systems prepared by powder metallurgy techniques and densi-fied in the presence of liquid phase, a precise analysis of microstructure and interfacial energy relationships requires a knowledge of the solid-solid interface energies and liquid-solid interface energies. However, marly metal-nonmetal systems are characterized by the "sweating" of the liquid during sintering, and in these systems wettability is a principal consideration. The wetting in turn is dictated by the various interface energies of the system, as shown in Fig. 1 for a liquid drop formed on a solid substrate. The equation which expresses the vectorial balance of surface forces in the horizontal plane, at the point of contact, A, is given by: where ssv = solid-vapor interface energy sSL = solid-liquid interface energy sLV= liquid-vapor interface energy 6 = contact angle measured through the liquid phase. The angle and the surface tension, slv, can be measured accurately by the sessile drop method.3, The absolute value of the surface energy of the solid cannot be determined by this method, but with reasonable changes in the composition of the liquid only, the value of ssv can be considered constant. The changes in contact angle, then, can be attributed to changes in sSL and sLV and since sLV can be measured, the changes in sSL can be determined. Several studies have indicated that the surface and bulk properties of solid alloys can be correlated with electronic structure. The catalytic activity of copper-nickel alloys was reported to follow the dband vacancies in these alloys.5 Nickel has been considered to have 0.6 holes per atom in the d-band. The addition of copper to nickel is thought to bring about a filling of the d-band of nickel, since each copper atom contributes one electron. Thus, at an atomic concentration of 60 Cu-40 Ni (62 wt pct Cu-38 wt pct Ni) the d-band is believed to be full, and magnetic measurements support this view.6 If the electronic structure is influencing a property of the alloy, this property should show some sort of discontinuity as the composition changes from one side of the 60 Cu-40 Ni composition to the other. Since the catalytic activity can be considered as a surface property of the alloy, it is logical to assume that other surface properties, such as surface tension, may also be influenced by electronic structure. The suggestion has been made that there is a correlation between the solid titanium carbide-liquid Cu-Ni alloy interfacial energy and d-band filling.7 One purpose of this investigation was to determine if the changes taking place in the electronic structure with compositional changes in the solid copper-nickel alloys were reflected in the surface tension values of the liquid alloys. Such a change, if present, would lend support to the suggestion that one can refer to discrete energy bands in the liquid state. Other purposes of the present study were to investigate in detail the wettability in the system copper-nickel-titanium carbide, and to discuss the possible processes which take place during wetting in this system.

Jan 1, 1961

By L. A. Roe, E. A. Elevatorski

Wollastonite, named after William H. Wollaston, an English chemist, is a calcium metasilicate, CaSiO3; CaO: 48.30%, SiO2: 51.70%. It has a short history as an industrial mineral. The earliest production of wollastonite is reported to be from a deposit near Code Siding, located north of Randsburg, CA. At this locality small tonnages of wollastonite were quarried during 1933-34 and 1938-41, and processed into mineral wool. This operation was largely experimental and virtually no United States production was again reported until the 1950s when a large deposit near Willsboro, NY, was developed by the Cabot Corp. A processing plant was placed onstream in 1953, with nearly continuous production to date. It is currently operated by NYCO, a division of Processed Minerals, Inc. Since 1958, wollastonite deposits in the Little and Big Maria Mountains of Riverside County, and in the Panamint Range of Inyo County, both in California, have operated intermittently for production of both ornamental and commercial wollastonite. During 1980, the United States was the major producing country, furnishing about 75% of the world's output. Current production comes from Finland, Mexico, India, and Kenya. Small amounts have been shipped intermittently from the USSR, New Zealand, Republic of the Sudan, Republic of South Africa, and Namibia (South-West Africa). The principal use of wollastonite is in the manufacture of plastics. Other uses are for paints, ceramics, adhesives, fluxes, glazes, thermal insulation board, and refractory products. Mineralogy Pure wollastonite, CaSiO3, has the composition of 48.3% CaO and 51.7% SiO2. However, it is seldom found in the pure state due to the ease with which it takes into solution the metasilicates of manganese, magnesium, iron, and strontium. Predominantly, wollastonite occurs as a contact metamorphic deposit forming between limestones and igneous rocks. Commonly associated minerals are garnet, diopside, epidote, calcite, and quartz. It has a specific gravity of 2.8 to 3.0, and hardness of 4.5 to 5 on Mohs' scale. When pure, it has a brilliant white color, but with impurities it may be grayish or brownish. Luster is vitreous to pearly. Melting point of wollastonite is about 1540ºC. Wollastonite occurs in coarse-bladed masses, rarely showing good crystal form. It is usually acicular or fibrous, even in the smallest of particles. The most unique property of crushed and ground wollastonite is its cleavage. Fragments of crushed wollastonite tend to be needle-shaped, imparting a high strength, and this property is the basis for many of its uses. The fiber lengths are commonly in the ratio of 7 or 8 to 1, length to diameter. The average diameter of wollastonite is 3.5 µm. Some crystals of wollastonite fluoresce under short-wave or longwave ultraviolet light, or both, with colors ranging from yellow-orange to pink-orange. Specimens may also show phosphorescence. The acicularity of wollastonite is a property of considerable importance to the marketplace. The plastics industry makes utilization of high aspect ratio grades of wollastonite (20:1) for reinforcing thermoplastics and thermoset polymer compounds. The naturally high pH of 9.9 (10% water slurry) is a prime property to the coatings industry. The coatings industry uses milled grades of wollastonite as a pH stabilizer in interior and exterior PVA and acrylic latex systems. Processed wollastonite can have a G.E. brightness of 90 to 93. Chemically, wollastonite is inert and this property makes it useful as a filler and reinforcing agent. There are two polymorphs of calcium silicates: wollastonite, a low temperature form, and pseudowollastonite, a high temperature

Jan 1, 1983

By S. T. Yuster

An analysis has been made of the factors responsible for tilted fluid contacts in petroleum reservoirs. The factors are static and dynamic with the former being controlled by those variables responsible for the capillary rise of fluids, and the latter include rate of formation tilt and hydraulic circulation. The explanation that rate of formation tilt may be responsible for tilted contacts appears untenable. The role of some of these factors in the migration, fractionation. accumulation and possibly the prospecting for oil is indicated. INTRODUCTION While it is generally considered that the segregation of gas, oil, and water in a petroleum reservoir results in approximately horizontal planes separating these phases. there are factor; which modify this simplified picture to a very great extent. Some of these factors are static. and the departure of the fluid interfaces from horizontal may represent a static equlibriun. Some of these factors may be dynamic and the interface positions may be non-equilibrium and represent a steady .state condition. Of course combinations of these two situations may also exist. The reasons most commonly given for this behavior are hydraulic circulation of fluids, change in character of the formation, and a rate of tilt of the formations more rapid than the rate at which the fluids may re-establish an equilibrium. Russell's Principles of Petroleum Geology' contains an extensive discussion of tilted fluid interfaces and their importance in the migration and accumulation of petroleum. Russell cites examples of tilted water tables at Lance Creek, Wyo.; Rock River, Wyo.: Cut Bank. Mont.; Cushing, Okla.: and Graham; Okla. Also given was the Wasson Field of West Texas which has saucer shaped oil-water and gas-oil interfaces with the saucer being deeper in the case of the oil-water contact. The Bradford Field in Pennsylvania has a tilted water table. San Ardo. Coalinga None and some other California field.; have tilled contacts. A recent paper by King Hubbert discuses the effect of hydraulic circulation of the water underlying the oil in a given stratun and it- implications in the accumulation of and drilling for the oil. The foregoing would indicate that tilted fluid interfaces are not uncommon and that it would be of importance to underbtand the forces which are responsible. Further. it would be of interest to examine certain idealized models of situations which may cause tilting with the thought in mind of deriving relatinnships between the important variables. These relationships may only hold exactly for the model* assumed but the results may apply semi-quantitatively to actual formations and at least indicate trends. The discussion will be divided into the effect of static factors and the effect of dynamic factors. STATIC FACTORS It has already been mentioned that one reason given for tilted contacts is a variation in formation properties. Specifically this is a change in the pore size of the formation capilaries. If the internal surface of the reservoir is preferetially wet by water, capillarity will cause the water 10 rise to a greater extent above the free water table in a small capillary than in a large one. Consequently the water-oil contact will be higher in the lower permeability sands than in the higher permeability sand.;. The free water table may be defined as the position the oil-water interface would take if capillarity were absent. Since the phenomenon is the capillary rise of water in an oil environment, a derivation of this shold give a relationship between the variables. Fig. 1 is an idealized model of the situation with a uniform bore circular capillary ubstitttting for the tortuous non.circular formation pore. The upward force.; on the column of water will be equated to the forces downward to give the equilibrium situation. forces upward = force downward where r is the radius of the capillary in ceritimetera. a is the interfacial ten4on oil-water in dynes per centimeter, 0 is the

Jan 1, 1953

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By M. A. El-Aouar

Drilling muds are complex colloidal systems. In an effort to analyze the physical properties that affect their performance at high temperature, an investigation was made of the hydrothermal stability of the monoionic hydrogen, calcium and magnesium forms of montmorillonite and attapulgite. Samples were heated to 400°1F in a simple autoclave and analyzed for cation exchange capacity, c-axis X-ray diffraction spacing and pH factor us sodium hydroxide titration dependence. Out of the six monoionic clay minerals tested, calcium montmorillonite and magnesium attapulgite showed the least base exchange capacities and were relatively unaffected to heat. It is concluded that, of the six clays studied, these two clays were the most suitable forms for use in drilling fluids. INTRODUCTION The drilling of deep wells is dependent upon the drilling mud, and problems frequently arise concerning the effect of mud temperature and prolonged heating. Drilling muds are complex colloidal systems. In an effort to analyze their behavior in deep, hot boreholes, it was thought desirable in this investigation to study suspension of pure, monoionic montmorillonite and attapulgite clays before and after hydrothermal heating. Chemically, clays are hydrated aluminum silicates, such as montmorillonites and attapulgites. The structure of montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. Attapulgite consists of double silica chains running parallel to the c-axis with the chains linked together at their longitudinal edges. The apexes of the tetrahedrons in successive chains point in opposite direc-tions.4,7,10 One of the most important characteristics of clay minerals is their property of sorbing certain anions and cations and retaining them in exchangeable state. The property of exchange capacity is measured in terms of milliequivalents (meq) per 100 gm of clay. The cation-exchange capacities are taken at pH 7 from titration curves which show the relation between pH and milliequivalents of added NaoH.9,11 The following are causes of cation exchange: (1) broken bonds around the edges of the silica alumina units would give rise to unsatisfied charges, which would be balanced by adsorbed cations; (2) substitution within the lattice structure of trivalent aluminum for quadrivalent silicon in the tetrahedral sheet and of ions of lower valence; and (3) the hydrogen of exposed hydroxyls may be replaced by a cation which would be exchangeable. The primary techniques employed to study the effects of hydrothermal treatment were titration curves and X-ray diffraction analyses. Titration curves were useful in characterizing the nature of the clay mineral surface and the stability of the various samples to attack by acid or alkali before and after hydrothermal treatment. X-ray diffraction analyses were used to determine changes in the nature and crystal structure of the minerals present and to determine the cations in exchange positions on the montmorillonite samples. EXPERMENTAL PROCEDURE PREPARATION OF SAMPLES Selected samples of Wyoming bentonite and attapulgite clay from mines along the Georgia and Florida border were purified by centrifugation to remove all particles larger than 2 microns. In preparing magnesium attapulgite, first a 1.00-normal solution of magnesium acetate was prepared. The pH of the solution was adjusted to 7.0 by adding magnesium oxide. One hundred grams of attapulgite clay were mixed in a blender for 30 minutes with the magnesium acetate solution. The attapulgite solution was left overnight, and then filtered in a Buchner funnel. The suspension was leached with further quantity of magnesium acetate solution and then washed with distilled water for 20 days, after which the filtrate was free from magnesium ions. The concentration of magnesium attapulgite in the clay slurry was adjusted and determined quantita-