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By John Mathews

SOMEONE has divided mankind into two groups: (1) those who have the willingness and imagination to weigh the future gain over against a present indulgence, and (2) those who cannot do so. The former have self-control, patience, foresight and a capacity for sustained effort. Those having these homely virtues become the, possessors of capital and hence employers of others. Those lacking these qualities and owning no capital must seek it from those of the first class, and therefore are employed by others. The human qualities, which divide men into two classes-employers and employed-are, however, capable of change by education, training, environment and by all agencies which tend to develop character. These words of the economist have stuck in my mind for many years and the more I see of men in my business contacts the more firmly I am convinced of their truth. The earth in some respects resembles its inhabitants. When we stroll over the fields and hills we are impressed by the unorganized masses of sand and rock which make up the ground beneath our feet. When by chance we come upon a bit of mineral matter in crystalline form we are impressed by its beauty and symmetry and probably have it polished and call it a gem. Gems constitute a minute portion of the earth's crust, and those intellectual gems, worthy of polish, who brilliantly reflect the incident rays of education and experience that have fallen upon them are few among the masses of mankind.

Jan 1, 1931

By W. S. N. Waring, E. C. Bain, E. S. Davenport

The more familiar compositions of both the iron-carbon-chromium' and the iron-carbon-tungsten2 systems have been investigated with a degree of thoroughness which has permitted the construction of their three-dimensional equilibrium diagrams; and it is probable that these equilibrium diagrams are sufficiently accurate for the present metallo-graphic needs. Strangely enough, in spite of their importance, the alloys of iron, carbon and manganese apparently have not been investigated in the same systematic manner, and so far as is known, no three-component equilibrium diagram for this system is available. Even iron-carbon-nickel alloys3 have been studied rather more thoroughly; for these the solidus and liquidus surfaces have already been determined, but the solid transformations in this, as in the manganese system, have not been reported systematically. The present paper deals with the constitution at equilibrium of a series of 36 iron-carbon-manganese alloys of commercial purity limited by 1.5 per cent carbon and 15 per cent manganese, a range of compositions including most of the manganese steels. The temperature range of melting has not been determined, nor has the high-temperature (delta iron) ferrite equilibrium been included in the study, it being considered that the more important characteristics of the manganese steels are their ordinary transformations in the solid state. The delta iron region is almost certain to be a small tetrahedron not very different in magnitude or contour from that in the iron-carbon-nickel diagram. It is probably true

Jan 1, 1932

By G. C. Wallick, W. R. Foster, J. G. Savins

Inasmuch as the differentiation and integration methods represent different modes of rheological analyses, a dual scheme of analysis using both methods should lead to a generalized method of data analysis. A dual differentiation-integmtion method of analysis is applied here to the Poiseuille flow of a variety of ideal Generalized Newtonian and viscoplastic models. Using machine-processing techniques, the result is a spectrum of response patterns which are expressed in terms of certain derivative functions. It is shown that these characteristic functions form the basis of a highly-sensitive analytic technique for optimizing the selection of the most appropriate functional relationship between shear rate and shearing stress. INTRODUCTION In the first paper of this series, Savins, Wallick and Foster1 presented an historical review of the salient features of the differentiation method of rheological analysis in Poiseuille flow, and also indicated how the method could be applied to problems involving plane Poiseuille flow. It was shown that the differentiation and integration methods, although basically not incompatible, do represent different modes of rheological analysis. This suggests that valuable background information regarding the probable response characteristics of real data obtained with the differentiation method can be obtained from an integration method-differentiation method analysis of the response of a variety of ideal rheological models. The present paper describes how this dual method of analysis has been applied to suites of idealized models representing a wide variety of Generalized Newtonian and viscoplastic behavior which have received attention at various places in the literature.

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period May 10,1917, to June 10, 1917. F. J. Anderson, Cali, Colombia. W. F. Jahn, Kirkland Lake, Ont., Canada. George J. Bancroft, Denver, Colo. W. McA. Johnson, Hartford, Conn. W. F. B. Berger, Denver, Colo. J. E. Jopling, Marquette, Mich. F. J. Brulé, Toronto, Ont., Canada. William Kelley, Vulcan, Mich. J. Murray Clark, Toronto, Ont., Canada. H. M. LaFollette, La Follette, Tenn. Will L. Clark, Jerome, Ariz.. Dorsey A. Lyon, Washington, D. C. G. H. Clevenger, Palo Alto, Cal. James F. Magee, Lancaster, Pa. Paul S. Couldrey, Sound Beach, Conn. M. Ortin, Nijni-Novgorod, Russia. C. W. Crispell, Kingston, N. Y. - C. H. Palmer, Jr., Los Angeles, Cal. George A. Easley, La Paz, Bolivia. Edison S. Pettis, ?Mill Valley, Cal. Bancroft Gore, Butte, Mont. Mortimer A. Sears, Paintsville, Ky. John B. Guernsey, Roanoke, Va. W. J. Uren, Houghton, Mich. Rush M. Hess, St. Louis, Mo. C. E. Visel, New Haven, Conn. E. Hibbert, Nickelton, Ont., Canada. Percy E. Barbour, has resigned his position as managing editor of the Engineering & Mining Journal, to accept the appointment of Deputy Superintendent of the New York State Troopers, with headquarters at Albany, N. Y., with the rank of captain.. He has also been commissioned as captain in the 22nd Regiment, N: Y. N. G., having been formerly 1st Lieutenant.

Jan 7, 1917

By F. C. Blare

THE best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld'schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide,† It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter-color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results. * Fresenius, Zeitschrift Air Anal. Chemie., viii, 1. †First noted by Parkes in the Mining Journal for 1861.

Jan 1, 1881

By C. D. Hall, F. E. Dollarhide

Fluid Ioss agent.s for crude oil and for water have been studied in dynamic tests. A treatment using a spearhead with a fluid loss agent followed by plain fluid appears feas ible in crude oil, but not in water. An equation for spearhead depletion shows that spurt loss relative to fracture width must be low, if the portion of spearhead fluid in the treatment is to be small. The presence of colloidal matter in crude oils aids the fluid Ioss agent. Unlike in kerosene, where flow limited the agent deposition, in crude oils the filter cake continually formed and leak-off declined. The volume-time relation varied somewhat for different crudes, but was best described by a square root of time function. Spurt loss was inversely proportional to agent concentration. After the fluid loss agent initiated the filter cake, the crude oil colloids built on it effectively. A 2-minute or a 5-minute spearhead with double the normal agent concentration gave the same fluid Ioss curve as the same concentration did for a 30-minute test. The agents tested in water gave fluid Ioss plots on which, for the first few minutes, volume was proportional to the square root of time, but later became proportional to time. For fracture area calculation the customary square root of time function is a satisfactory approximation. Leak-off rates and spurt losses were higher in water systems than in oils. The spurt Ioss tended to be inversely proportional to concentration. In spearhead tests, the filter cakes were not eroded by water flow. However, the rather high spurt loss values make spearhead treatments impractical for water-based fluids. Introduction The effects of dynamic testing conditions on the performance of fluid loss agents in kerosene have been studied previously.' We have extended the work to include crude-oil- and water-based fracturing fluids. An understanding has been gained of the mechanisms of formation and functioning of the filter cakes of fluid loss agents. The practical aspects of evaluating performance of agents in relation to fracture area calculations also are considered. The feasibility of using the fluid loss agent in a spearhead stage of the treatment is examined further for both types of fluids. Experimental Procedure The dynamic fluid loss tests were performed in an apparatus similar to the high-pressure apparatus described in a previous publication.' A fracturing fluid was circulated over a rock surface located in a closed pressurized loop. The fluid flowed axially over the cylindrical surface of a core 2 in. in diameter X 3.5 in. long, mounted (with the flat ends sealed off) in a pipe, with 0.117 in. annular clearance. The filtrate was collected in a central hole in the core and led through valves to graduated cylinders. Provision was made for changing quickly the circulating fluid during the test (spearhead runs) without interrupting the filtration pressure. The only modifications were to add heating tapes and water jackets for the tests with crude oils, all conducted at ISOF, and to change all parts exposed to the test fluid to stainless steel for the tests with water-based fluids. The latter tests were made at room temperature, 80F. Three crude oils were tested. A mixed crude, obtained from a local refinery, contained a considerable amount of light ends. For safety reasons, it was stripped to 250F vapor temperature before use in the fluid loss tests. The other two oils were used as obtained from lease tanks. One was a greenish-brown, 37" API paraffinic crude, and the other was a black, 32" API asphaltic crude. The fluid loss agent for oil, here designated for brevity as Agent A, was Adomite@ Mark II*, a granular solid commercial agent, the same as previously tested in kerosene.' Three different compositions of fluid loss agents were tested in Tulsa tap water. Agent B was adomit& Aqua*, a solid commercial fluid loss agent, comprising clays and hydrophilic gums principally derived from starch. Agent C was a mixture of three parts of Agent B with two parts of silica flour. Agent D was Dowel1 J137, a mixture of guar gum and silica flour. The test cores were cut from contiguous blocks of Berea or Bandera sandstones. For the oil tests, the cores were oven dried, evacuated, saturated with kerosene, and the kerosene permeability was measured. The cores used with the water-based fluids were pretreated by saturating with 3 percent calcium &loride solution to minimize pemeability damage by the fresh water due to clay migration. The

Jan 1, 1969

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall's work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann's approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen's approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By J. R. Vilelia

IN accordance with the custom of this society, we are gathered here, as we have every year since 1924, to honor the memory of the eminent American metallurgist and teacher, Professor Henry Marion Howe. Unlike many of the distinguished metallurgists who have preceded me as a Howe lecturer, I cannot bring to you reminiscences of his personality, for it was not my privilege to be associated with Professor Howe, or to be directly one of his students. Yet, Professor Howe and Professor Albert Sauveur, through the medium of their books, were my first teachers of metallography, as they have been of almost all American metallurgists of my generation. As a teacher, and for many years the acknowledged leader of American metallurgists, he exercised a profound influence in the growth of our science and was held in honor by the men of science of his time. I can speak no words of technical appreciation that will add luster to his fame, for by his prophetic vision, his teachings, and his researches he stands among the immortals in the memory of all metallurgists. In 1926, the third Howe Memorial Lecture was presented by Professor William Campbell' of Columbia University, who entitled it "Twenty-Five Years of Metallography." He took as a starting date for his chronology the turn of the century, which coincided with his arrival from England to work in association with Howe at the Columbia School of Mines. In that informative lecture Professor Campbell enumerated the important advances in metallography achieved during the first quarter of the century, and, it now appears, may have established the custom of reviewing such progress every twenty-five years. The scope of Professor Campbell's lecture was as broad as his metallurgical knowledge, for it embraced a wide portion of the field of metallography, both ferrous and nonferrous. Twenty-five years later, the Howe Memorial Lecture Committee saw fit to assign to me the honor of writing a lecture that would commemorate the work of Henry Marion Howe and would at the same time constitute the 25th anniversary of the lecture by Professor Campbell. The Committee suggested that this lecture might properly be called "Twenty-Five More Years of Metallography," a suggestion that I have adopted. I must confess, however, that I have not followed the precedent established by Campbell and have narrowed the scope of this lecture to an appraisal of those achievements which in my opinion have contributed most to the progress of microscopical metallography during the past twenty-five years. Progress in Metallography The metallographic methods most widely used today, with the exception of the electron microscope, were firmly established more than twenty-five years ago. In general, our specimens were prepared for microscopic examination in those days in much the same manner as they are today. It is true that new details of technique have been introduced from time to time, and that superior equipment is available today, but on the whole, these improvements have been in the nature of refinements, often a matter of personal preference, and none can be considered essential to the attainment of the ultimate goal of the art and science of metallography, which is to reveal the structure of metallic specimens with unequivocal clarity so that they may be interpreted correctly. Mechanical metallographic polishing, which was the only method available in 1926, is still universally practiced and still consists of abrading the metallic specimen with a series of abrasives of increasing fineness until a specular surface is attained. We have now the alternative method of electropolishing, but it is not widely used because, except in a few special cases, its results are inferior to those of competent mechanical polishing. Likewise, most of the etching reagents preferred today were in common use more than twenty-five years ago and were applied in the same manner as they are today. Valuable improvements have been made in the optical and mechanical performance of metallurgical microscopes, but there was no dearth in those days of excellent instruments equipped with achromatic and apochromatic objectives capable of yielding micrographs comparable in quality with the best that we can make today. In fact, it would be a difficult task for any metallographer today to make optical micrographs at magnifications in excess of 3000 diameters that would surpass those made by Lucas more than twenty-five years ago. One of these is shown in Fig. 1. Yet, it is unquestionable that on the whole, the micrographs appearing in the metallurgical literature today are vastly superior to those

Jan 1, 1952

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By R. G. Agarwal, Ramey Jr. H. J., Al-Hussainy R.

Although it has long been realized that gas recovery from a water-drive gas reservoir may be poor because of high residual saturations under water drive, it appears that only limited infomlation on the subject has been available until recently. This study was performed to show the qiiantitative potential importance of water influx. Results indicate that gas recovery may be very low in some cases: perhaps as low as 45 per cent of the initial gas in place. Gas recovery under water drive appear to depend in an important was on: (I) the prodirction rate and manner of production; (2) the residual gas saturation; (3) aquifer propertie.); and (4) the volumetric displacement effciency of water invading the gas reservoir. The manner of estimating water-drive gas reservoir recovery can vary considerably. Examples are: the steady-state tnethorl. the Hurst modified steady-state method, and various unsteady-state methods such ac. those of van Ever-dingen-Hurst, Hurst, and Carter-Tracy. The Carter-Tracy water influx expression was used in this study. In certain cases, it appears that gas recovery can be increased significantly by controlling the production rate and manner of production. For this reason, the potential importance of water influx in particular gas reservoirs should he investigated early to permit adequtrtr planning lo optirtize the pay reserves. INTRODUCTION In recent years, the economic importance of natural gas production has become increasingly apparent. This has been evidenced by more intensive exploration efforts aimed at gas production, and exploitation of both deep, as well as low-permeability gas reservoirs. Technical developments such as deep-penetration fracturing have made development of such formations economically feasible. Unfortunately, water influx has forced abandonment of a number of gas reservoirs at extraordinarily high pressures. Although reservoir engineering methods for estimating water influx have long been available, it appears that application of these methods to the water-drive gas reservoir has been sporadic.'a Available methods for estimating water influx which can be applied to the water-drive gas reservoir problem include the steady-state method,1 the Hurst modified steady-state method and various unsteady-state methods such as those of van Everdingen-Hurst. Hurst, and Carter-Tracy. Interesting applications of these solu- tions to gas reservoir and the aquifer gas-storage problems have appeared recently.3,12,14 The experimental study of residual gas saturations under water drive by Geffen et al. in 1952 indicated that residual gas saturations could be extremely high. A value of 35 per cent of pore volume is often used in field practice when specific information is not available. The study of Geffen et al. showed that residual gas saturation might be much higher in some cases. Naar and Henderson concluded that the residual non-wetting phase saturation under imbibition should be about half of the initial non-wetting phase saturation. The Naar and Henderson result that residual gas saturation under water influx should be about half the original gas saturation is recommended as an estimate if laboratory measurements are not available. Thus, it is clear that a considerable portion of the initial gas in place might be trapped in a water-drive gas reservoir as residual gas at high pressure. A full water-drive would result in loss of residual gas trapped at initial reser.voir pressure. Consideration of transient aquifer behavior leads to the conclusion that high-rate production of water-drive gas reservoirs could result in improved gas recovery by reduction of the abandonment pressure. However, there appears to be little quantitative information on this possibility. One of the few advantages of water-drive gas production appears to be improved deliverability through water-drive support of the reservoir pressure. There may also be an advantage in higher condensate recovery caused by pressure maintenance for gas-condensate water-drive reservoirs. In view of the preceding, this study was made to assess the potential importance of water-drive in gas reservoir engineering. The Carter-Tracy approximate water-influx expression was used because this equation offers some advantages in hand-calculation which do not appear to have been generally recognized.' However, calculations were performed in the main with a high-speed digital computer to permit evaluation of the effect of water-drive under a large variety of conditions. CALCULATION METHOD Water-drive gas reservoir performance can be estimated in a manner completely analogous to oil reservoir calculations: a materials balance is written for the reservoir, and a water influx equation is written for the aquifer. Siniltaneous solution provides the cun~ulative water influx and the reservoir pressure. When reservoir performance data (gas produced and reservoir pressures) are available, it is usually possible to match performance data to determine the initial gas in place and the water influx parameters —

Jan 1, 1966

By Werner Schwartz, Wolfgang Haase

Lead sulfide concentrates, which may include other lead concentrates, are sintered on an up-draught sintering machine without the addition of any diluting agents or fluxes. Subsequently they are melted in an oil- or gas-fired rotary furnace. The sintering and melting processes are based upon the following roast-reaction: PbS + 2 PbO = 3 Pb + SO, PbS + PbSO, =2 Pb + 2 SO, For obtaining a lead bullion free from sulfur, the sintering process is carried out in such a way that the sinter product contains a small amount of excess oxygen above that to react with the sulfides. At the end of the melting process, when the reactions are finished, the remaining small amount of oxide residues is reduced with coal to which a certain percentage of soda ash (about 1 pct of the lead bullion) is added. For the lead smelting process described neither coke nor fluxes—except soda ash—are required. This process is being utilized by a European smelter successfully and with a high lead recovery. The consumption figures for the smelting of 100 tons per day of lead concentrates are indicated. The lead content of the lead concentrates from modern ore dressing plants ranges from 65 pct to above 80 pct. In most lead smelters of the world these concentrates are smelted in a blast furnace. For blast-furnace smelting the concentrates have to be desulfurized and agglomerated by sintering. A requirement for the perfect operation of a down-draught sintering machine and of a blast furnace is a maximum lead content in the feed of 40 to 45 pct. For this reason, some lead concentrates have to be diluted by adding return slags, limestone, and possibly iron oxide and sand. As an example, 100 tons of lead concentrate with 72 pct Pb would contain 13.5 tons of gangue (including the zinc). To produce a perfect sinter with 42 pct Pb it would be necessary to add 70 tons of flux and return slag, more than five times the original weight of the gangue, to the sinter mix and blast-furnace charge. A correspondingly large amount of coke would be required in order that all of these materials reach the heat of formation and the melting temperatures of the slag (1200" to 1400°C) inside the blast furnace. The roast-reaction process presents a possibility for lead recovery without dilution of the concentrates. In this process the concentrate mixed with coal is placed upon a Newnam-hearth and air is blown through nozzles into the heated mix. AS a result metalllic lead and a relatively great amount of so-called .'Grey Slag" with a lead content of 25 to 35 pct are formed. The slag is sintered to eliminate sulfur and, after addition of the requisite fluxes, treatt:d in a blast furnace. Owing to the poor recovery of lead from the hearths and to the unavoidable heavy hand-work plus the risk of poisoning this process is utilized in very few 112ad smelters today. Since in mxny countries of the world coke is expensive and difficult to obtain, it appeared feasible to use the principle of the roast-reaction by modern sintering and melting methods with recovery of the lead in electric, or oil, gas, or coal-fired furnaces. Two processes are utilized on an industrial scale: A) Lead smelting in the electric furnace of the Bolidens Gruv A/B in Sweden, as described by S. J. Walldcn, N. E. Lindvall, K.G. Gorling, and S. Lundquist. B) The self-fluxing lead smelting of Lurgi Gesell-schaft fiir Chemie und Huttenwesen m.b. H., Frankfurt a M, Germany, which is described in this paper. In the Boliden process referred to above the sinter mix is pelletized by enveloping return fines with layers of flue dust, limestone powder, and dried galena concentrate. The roasting and agglomeration are carried out on a down-draught machine, and a slight excess of sulfur is left in the sinter product. During the smelting in the electric furnance the roast-reactions occur and a slag poor in lead and a sulfur bearing lead are formed. This latter is subsequently oxidized in a converter to obtain lead bullion and dross. The Lurgi-process achieves the maximum possible extent of the roasting reaction on the sintering machine. The wet flotation concentrates are blended with return fines (lead content 70 to 80 pet), any existing flue dusts and lead slimes—but without the

Jan 1, 1962

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at '750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By D. A. Augenstein, L. V. Amundson

Operators of coal preparation plants use equipment such as large-capacity dump trucks and bulldozers to haul, spread, and compact refuse material to conform to federal and state regulations governing the disposal of solid waste. For example, federal regulations require that refuse be spread and compacted in layers not more than 0.6 m (2 ft) thick. If the refuse layers or piles have poor load-bearing characteristics, movement of equipment over them becomes extremely difficult. The increasing cost and limited space for the construction of settling ponds extensively used for fine refuse disposal are leading to the growing practice of dewatering the fine refuse by means of vacuum disk filters and combining the resulting filter cake with coarse refuse for waste bank disposal. However, this filter cake usually contains more than 25% moisture. Therefore, when it is combined with coarse refuse, the moisture level of the total refuse may become high enough to impair the load-bearing strength of the refuse. Precisely this problem and the attendant difficulties of moving heavy equipment arose when vacuum disk filters were installed at a preparation plant in West Virginia. Combining the moist filter cake with the coarse refuse generally results in a 12% moisture level for the total refuse at this plant. At this moisture level, the refuse can still be handled with some dif¬ficulty by the equipment. However, the problem has frequently been compounded after rains. The experimental program described in this paper tested the following methods of improving the load-bearing properties of coal refuse: moisture reduction, addition of crushed coarse refuse, addition of fly ash, addition of lime, and addition of a mixture of lime and fly ash. In terms of a balance between economic and technical considerations, the most effective method was demonstrated by laboratory and plant tests to be a 2% to 5% addition of lime. Test Program During formulation of a test program aimed at improving coal refuse stability, a number of treatment techniques were selected for evaluation of their effect on refuse load-bearing characteristics. The reduction of refuse moisture was the first technique considered, since moisture content plays a key role in the bearing strength of a bulk solid. The reasoning was that a very small reduction in refuse moisture, provided it could be accomplished with minimal effort and cost, would be sufficient for eliminating refuse disposal problems most of the time. At the same time, it was recognized that periods of rainy weather would offset moisture-reduction measures. Other techniques selected for evaluation because of their potential for improving refuse-bearing strength at reasonable cost were: addition of crushed coarse refuse, the addition of fly ash, and the addition of lime. A simple one-dimensional laboratory compaction test was designed for evaluating the effect of each of these techniques on refuse-bearing strength. Those techniques that gave best results in the laboratory would then be tested in the preparation plant in West Virginia. Laboratory Tests The laboratory test for evaluating each of the techniques involved the application of weight to a load module placed on a refuse sample in a container. The distance the load module sank with an increasing amount of applied weight was measured, and the relationship between module displacement and loading was obtained. The refuse container was large enough to minimize the influence of wall effects, and to decrease the effect of the container bottom, a test was terminated when the load module sank to about three fourths the depth of the container. Initially, an attempt was made to conduct compaction experiments with samples of total plant refuse. However, the presence of + 0.13 m (+ 5 in.) material in the refuse interfered with the mechanics of the test, and the large amount of material required for a representative sample made testing extremely tedious and time-consuming. To avoid this problem and because it was believed that only the fine components of the refuse were the major cause of the stability problem, tests were conducted with 13 mm X 0 (1/2 in. X 0) material from the total plant refuse. The equipment consisted of a 0.46 m (18 in.) cubic container, a loading module with 62 cm2 loading area, weights totaling 450 kg, and a portable concrete mixer for combining water and additives with the refuse. Refuse samples of about 110 kg dry weight were used for each test. Experimental compaction test data were evaluated by plotting the linear displacement of the load module vs. loading. During compaction tests, the vertical displacement of the load module was measured at each loading value. The plot of

Jan 1, 1980

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,1 and they seem, indeed, to diffract as individuals causing the Hull pattern of a, severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles determined by the manner and intensity of cold working.

Jan 1, 1927

By David Mitchell

MANY of the difficult operating problems of the preparation of coal for market, of sampling coal shipments and in the utilization of coal are caused by segregation in the coal mass. Segregation may be of two kinds: i.e., "size segregation," in which parti- cles of the same size in a mass of coal containing a range of sizes collect to-gether and "density segregation," in which particles of the same density or specific gravity in a mass of particles of varying density gather together. MECHANICS OF SEGREGATION Size segregation cannot take place with closely sized coal. As the size range increases, the tendency for size segregation increases. Similarly, cleaned coal with particles of approxi- mately the same specific gravity have very little tendency for density segrega- tion. The wider the density range of particles and the more particles of different density, the greater the chances are for density segregation. FIG. 1.-SEGREGATION IN A SIDE-FILLED The following discussion deals primarily BIN with coal of a wide size range as screenings and of wide density differ-ences as uncleaned or run-of-mine screenings. If a mass of coal containing particles of a wide size range is subject to the stream action of a moving current of water, the small particles are transported farther than the coarser. Particles of different density in a stream of moving water are subject to the laws of classification, the heavier settling out first. The familiar sluice box of the gold miner and the action of rivers and other streams in classifying material according to

Jan 1, 1937

By Alden B. Greninger

That metallographic structures analogous to the martensite of steel may be found in certain copper-aluminum and copper-tin alloys has been known for many years; similar structures recently were found in certain copper-zinc a1loys.l In all three of these alloy systems the martensite structures result from transformation of the metastable fi phase when the speed of cooling from the B range is sufficiently high to suppress decomposition into equilibrium phases. In the normal decomposition of solid solutions into equilibrium phases, diffusion is needed to bring about the necessary changes in concentration, and the rate of reaction falls almost to zero at temperatures slightly above room temperature. The rates of reaction for martensite processes, however, are not dependent upon temperature; the transformation does not require rendjustments of concentration. For example, the martensite transformation in 60:40 (B) copper-zinc does not begin until the temperature has dropped to about minus 30" C., and then continues down to minus 130" C. and probably even at lower temperatures.' Furthermore, martensite processes apparently proceed only while the tempcrature is falling, within the proper range, and cease completely while the temperature is held constant ;$ and they cannot be suppressed by extremely rapid cooling although the rate of cooling for some alloys may be increased to over 10,000 times the critical cooling velocity. Isaitschew, Kaminsky and Kurdjumow2 account for these observed behaviors of rnartensite processes by postulating that the mechanism 6I... consists in a regular rearrangement of the lattice in such a way

Jan 1, 1939

By Alden B. Greninger

That metallographic structures analogous to the martensite of steel may be found in certain copper-aluminum and copper-tin alloys has been known for many years; similar structures recently were found in certain copper-zinc a1loys.l In all three of these alloy systems the martensite structures result from transformation of the metastable fi phase when the speed of cooling from the B range is sufficiently high to suppress decomposition into equilibrium phases. In the normal decomposition of solid solutions into equilibrium phases, diffusion is needed to bring about the necessary changes in concentration, and the rate of reaction falls almost to zero at temperatures slightly above room temperature. The rates of reaction for martensite processes, however, are not dependent upon temperature; the transformation does not require rendjustments of concentration. For example, the martensite transformation in 60:40 (B) copper-zinc does not begin until the temperature has dropped to about minus 30" C., and then continues down to minus 130" C. and probably even at lower temperatures.' Furthermore, martensite processes apparently proceed only while the tempcrature is falling, within the proper range, and cease completely while the temperature is held constant ;$ and they cannot be suppressed by extremely rapid cooling although the rate of cooling for some alloys may be increased to over 10,000 times the critical cooling velocity. Isaitschew, Kaminsky and Kurdjumow2 account for these observed behaviors of rnartensite processes by postulating that the mechanism 6I... consists in a regular rearrangement of the lattice in such a way

Jan 1, 1939

By V. F. Hollister

Although it is apparent that porphyry copper deposits may have formed in the Andean orogen from Permian time onward, commercial deposits thus far developed appear to have Cenozoic ages only. Following Chilean usage, the porphyry deposits are divided into either (1) a stockwork or (2) a tourmaline breccia model. As indicated by evidence cited in the paper, stockwork-type deposits tend to be related to major strike-slip structures which may be either transcurrent or transverse faults related to plate movements, while the tourmaline breccia type may more frequently form independently of regional faults. Stockwork types may be conjugate fractures that intersect and ramify as a network of veins and veinlets, cutting altered rock, and genetically related to a major regional fault, or in other cases they may reflect the intersection of two large fault structures. Circular fracture patterns may more rarely occur in stockwork deposits in response to a specific intrusion. Tourmaline breccia types are characterized by circular and radial fractures genetically connected in some way with touramline breccia pipe development or an intrusive piercement that preceded it. Each structural model contains mineralized intrusions which have a close time-space relationship to ore, and in each model mineral paragenesis is similar, regardless of age or location in the plate. Also, each model contains the same type of alteration halos (phyllic, argillic, propylitic) as are developed in intrusive centers in porphyry copper deposits found in North America. The potassic zone is exposed best in the older deposits. Examples of each type of deposit are illustrated, demonstrating the feature evolved.

Jan 1, 1975

By E. P. Mathewson

The early development of the reverberatory furnace for smelting copper-ores was the work of the Welsh smelters, particularly those of Swansea. The first record of a reverberatory furnace is made by Jars, who states that in 1755 copper-smelting was effected .in reverberatory furnaces at Middleton-Tyas, in Yorkshire, England. The first patent, of any importance, for improvements in reverberatory furnaces was granted to Thomas Williams in 1778 for the granulation of the regulus. The next was that of William Evetts, in Sheffield, in 1812, for the cooling of the fire-bridge by the admission of air. Charge-hoppers above the furnaces were in common use in 1848. The size of the hearth of the furnaces about the beginning of the 19th century was commonly 11 by 8 feet. No material development was made until the Welsh process mas brought to Colorado, where Richard Pearce, as manager of the Argo works, near Denver, developed the furnace to meet the requirements of a custom plant, under keen competition with lead-silver smelting-plants, using blast-furnaces. His improvements are outlined in Fig. 1, elaborated by permission from E. D. Peters's excellent work,' to which the reader is referred for further details. This figure shows that the furiiaces were in 1878, 9 ft. 8 in. by 15 ft. in hearth; and in 1894, 16 by 35 ft., while the capacity of the furnace had been increased from 12 tons per 24 hr. to 50 tons in the same period.

Jan 1, 1913

COMPARED with the equipment used in most industrial processes, the open-hearth furnace has a relatively short life. The most important quality of an open-hearth refractory, therefore, is its rate of failure. This discussion of the physics and chemistry of the individual refractory materials will keep uppermost the question "Why, how, and where does it fail?" CAUSES OF FAILURE The principal causes of failure of open-hearth refractories are, in their order of importance : 1. Reaction with iron oxides. 2. Reaction with slag. 3. Flow and failure under load. 4. Melting. 5. Spalling. 6. Mechanical breakage. Reaction with Iron Oxides and Slag. Reaction with iron oxides and slag is by far the most important cause of failure. Liquid iron oxide comes near to being the "universal solvent" sought for by the alchemists. Among the materials commonly used in the open-hearth furnace, magnesia has the greatest resistance to this liquid and fireclay the least. The relations of iron and oxygen at high temperatures are illustrated in Fig 14-18. The liquid iron oxide that forms wherever iron is in contact with air or combustion gases cannot be given a definite formula. The percentage of oxygen at steelmaking temperatures may range from 21 to 28 (iron 79 to 72), depending upon the temperature and the oxygen pressure and also upon whether or not the liquid is in equilibrium with metallic iron. Oxide mixtures exist not only in the solid and liquid phases but also in the vapor phase, for metallic iron and its oxides have

Jan 1, 1964