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By Henry E. Wood

In my opinion, the concentration of minerals by flotation is the most interesting problem in ore-dressing, and will command eventually far more consideration than it has at present. For many ores it furnishes a complete method of concentration absolutely independent of specific gravity, and thus simplifies the milling of many difficult combinations. Not having to recognize the influence of specific gravity, we are also able to dispense with some of the complications resulting from classifying-conditions. Where flotation cannot be used for a complete separation of the minerals from the gangue, it will be found, in nearly all cases, to save those portions which are generally lost by reason of their fine state of division. For this reason, it should be looked upon mainly as an aid to general concentration, although there are many ores so well adapted to flotation that more than 90 per cent. of the valuable metals can be recovered from them in one operation by this process. In presenting the results of my investigations in flotation, I have endeavored to theorize as little as possible. That side of the subject has been extensively discussed by others. My earliest work with flotation was done in 1895, when I used various oils, grease, soap, etc., with results that were remarkable. I did not realize then that with water alone equally good separations could be made. Up to 1906, my endeavors were confined to attempts to keep the concentrates on the tables well wetted and away from exposure to the air. In common with others, I observed that when there mas any obstruction in the wash-water on the table of sufficient size to divert the water to either side, the concentrates collected, and, on exposure to the air, would promptly float away. This convinced me that the sulphides were all good "swimmers," and that if,

Jan 1, 1913

THE Copperton mill in reality was a sort of proving ground. It was. designed to serve three purposes: (1) to verify the accuracy of the mine sampling by actually treating substantial tonnages of ore, (2) to demonstrate on a reasonably large scale the percentage of the copper in the ore that could be recovered, and (3) to permit the testing of various kinds of machines and devices for crushing and concentrating the ore, so as to guide the engineers in designing the proposed 6000-ton milling plant at Garfield. As a matter of fact, it contained a lot of second-hand equipment sent by MacNeill and Penrose from the works of the United States Reduction &Refining Co. in Colorado; and it was by no means a model installation. Probably it would have been even less efficient, except for the skillful work of George O. Bradley and-Frank-G, Janney, both of whom had worked with Jackling at Mercur. Bradley was a mechanical engineer employed to design the plant. Later he directed the design of the concentrator at Garfield and remained as consulting mechanical engineer to the company until 1915. Janney, who afterwards became manager of mills, a position that he retained until his death in 1916, was a skilled mechanic at the Golden Gate mill at Mercur when Jackling built the plant in 1897. His flair was making machinery do what it was intended to do. He was not an ore-dressing engineer in a technical sense; but Jackling him- self was a specialist in this respect as well as in designing and construction and Janney's mechanical aptitude made him a particularly valuable man in the Utah organization. John McDonald, another of Jackling's Mercur associates, was the first mine superintendent. With practically all of the available funds earmarked for construction of the Copperton

Jan 1, 1933

By E. D. Levine

A study was made to delineate the dislocation mechanistns controlling prismatic and basal slip at low temperatu.ves in titanium containing approximately 100 ppm interstitial impurities. Mechanical tests were performed on single crystals prepared from electron-beam zone-refined crystal bar by a thermal cycling technique. Measurements were made of critical shear stress and activation volume as functions of temperature. The study revealed that, for prismatic slip, two overlapping thermally activated processes aye rate-controlling below 300°K. From absolute zero to 220°K, reasonable agreement is obtained between experiment and the mechanism which involves overcoming 01. the Peierl's stress by the formation of double kinks in dislocation lines lying in close-packed directions. Between 220°and 300°K prismatic slip is controlled by a difierent thermally activated process which is characterized by a stronger temperature dependence of critical shear stress. Above 300OK, prismatic slip is controlled by an athermal process. Basal slip is controlled by a thermally activated process between 195' and 400°K. An approximate analysis suggests that it is the Peierl's mechanism that is rate-controlling in this range. Below 195°K, the occurrence of mechanical twinning obscures the features of basal slip. Above '400 X, basal slip is controlled by an athermal process. TITANIUM, an hcp metal with a less-than-ideal axial ratio of 1.587, deforms primarily by {1010}( 1210) slip at low temperatures.'-3 The critical shear stress is strongly affected by the presence of interstitial impurities. For example, churchman3 reported that a decrease in the combined nitrogen plus oxygen content from 0.1 to 0.01 pct decreased the critical shear stress for prismatic slip from 9.19 to 1.4 kg per sq mm at room temperature. Basal slip, however, is less strongly affected by interstitials; Churchman's data for {0001}( 1210) slip show a smaller decrease in critical shear stress from 10.90 to 6.3 kg per sq mm at room temperature, for the same decrease in interstitial content. In the present study, an attempt has been made to delineate the dislocation mechanisms controlling prismatic and basal slip in titanium. In view of the strong effects that impurities may have on at least some of these mechanisms, experiments were performed on material of reasonably high purity, so that comparisons could be made with investigations on material of both lower and higher impurity contents. EXPERIMENTAL PROCEDURE Single crystals were prepared from 1/4-in.-diam electron-beam zone-refined crystal bar, furnished by Materials Research Corp. The analysis of the zone-refined material is given in Table I, indicating that the interstitial content is of the same order as the purer of the two materials investigated by Churchman. The Vickers diamond pyramid hardness number of this material was 85.6. This value agrees quite well with the correlation between hardness and interstitial content proposed by Ogden and Jaffee.4 On the basis of hardness, the material investigated in this study is, therefore, intermediate in purity between that studied by Churchman (Vpn = 97) and that studied by Spangler and Herman (Vpn = 62.4).5 Single crystals were grown by thermal cycling through the a-ß transformation. Two-in.-long by 1/2-in.-diam bars were heat-treated in vacuum for 4 hr at 1160°C. The temperature of the furnace was then lowered to 865°C, and the specimens were maintained at this temperature for 7 days. This procedure was repeated several times, resulting in the growth of individual crystals up to 14 in. in length. Specimens for testing in direct shear along either {l010}(1210) or {0001}(1210) were obtained by electrical-discharge machining. The specimens were in the form of cylinders 1/4 in. in diam by approximately 1/2 in. in length, with a reduced section 1/8 in. in diam and a in. in length. All specimens were electropol-ished subsequent to electrical-discharge machining. The ends of the test specimens were cemented in stainless-steel collars. Shear tests were conducted in an Instron Tensile Tester at various temperatures from 4.2° to 508°K. Measurements were made of critical shear stress and activation volume. The latter measurements were performed by measuring the change in flow stress upon cycling the strain rate between ?1 = 2.62 x 10-3 per sec and ?2 = 2.62 x 10-4 per sec. Activation volume, I)*, is defined as u* =ßkT [11

Jan 1, 1967

By Frederick Görannsen

McDuffie county, once a part of Columbia county, lies in the eastern part of central Georgia, about 20 miles west of the Savannah river, and bounded on the northtwest by Little river. Wrightsboro, now almost forgotten, was one of the principal towns of Georgia before the Revolutionary war, and much of the land hereafter described as belonging to one of the principal gold-bearing sections of the South had been taken up by the early agricultural settlers, and was already under cultivation. Indeed, some of the present mining companies can trace their chain of title back to the original grant of King George III., made in 1771. The first discovery of gold in Georgia, however, was not made until 1823, when two English miners, who had emigrated to this country and were traveling as peddlers through this section, discovered quartz, rich in gold, on what is now known as " the 40-acre lot," and owned by the Columbia Mining Go. These men had no money to buy the lands, and not being able to stake off a claim and begin work, as is the custom in other places, they were forced to seek the aid of the native farmers. In this we are told that they were for a long time unsuccessful; the farmers and land-owners not knowing or caring anything about gold mining. In 1826, Jeremiah Griffin, a wealthy farmer, became interested with them, and they did some prospecting and located several rich veins. Mr. Griffin soon became enthusiastic, and bought about three thousand acres of supposed gold-lands, lying along Little river.. This purchase was unfortunate for the mining industry, as it effectually shut out all other prospectors, and confined entirely to Mr. Griffin and his associates the mining development of the whole region. As a consequence, the ground was never covered, arid there are virgin lands in this section now, which offer to the prospector as

Jan 1, 1903

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-' mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz' for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By AIME AIME

THE program of government drilling, conducted jointly by the U. S. Geological Survey and the Bureau of Mines, has demonstrated the presence in Texas and New Mexico of potash-bearing beds of considerable importance. Information regarding the ex- tent and location of the potash deposits as presented at the non-metallic sessions was of great interest to many engineers. These subjects will be covered in greater detail in later paragraphs. The first session, with about 50 in attendance, convened at 10 a.m. on Feb. 18, with Oliver Bowles, chair- man of the Committee on Non-Metallic Minerals, pre- siding. The first paper was on "Soapstone Mining In Virginia," presented by C. W. Ryan of Lynchburg, Va. The nature and extent of the soapstone deposits of Nelson County were described in some detail. In origin, the soapstone is undoubtedly related to a basic peridotite rock though its mode of formation is some- what uncertain. This main soapstone deposit occurs in three veins, the western, middle, and eastern, the middle vein being of greatest economic importance. Methods of stripping, quarrying and milling the rock were described and the uses of soapstone were enum- erated. In discussing this paper, C. P. Berkey, of Co- lumbia University strongly favored the theory of igneous origin of the soapstone and the need for further detailed geological study. J. L. Gillson of Cambridge, Mass., stated that the Vermont and New York talc deposits were always associated with characteristic minerals, such as, a chlorite of one particular variety, siderite, amphibole, magnetite, and biotite. C. H. Behre of Cincinnati, Ohio, raised the question of parallelism in the soapstone structure and Mr. Ryan stated that such parallelism was in evidence in some parts of the deposits. H. A. Wheeler of St. Louis, Mo., also took 'part in the discussion.

Jan 1, 1929

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By M. Cohen, R. T. Howard

It has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkinl has shown that the compositions of two coexisting phases in a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanaly-sis. Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantita-tive way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of this research could not be treated satisfactorily by other quantitative tools, such as specific volume,' magnetic,6 dila-tometric, electrical resistance7 or x-ray measurements.a It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. Literature Survey Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1948

By M. Cohen, R. T. Howard

It has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkinl has shown that the compositions of two coexisting phases in a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanaly-sis. Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantita-tive way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of this research could not be treated satisfactorily by other quantitative tools, such as specific volume,' magnetic,6 dila-tometric, electrical resistance7 or x-ray measurements.a It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. Literature Survey Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1948

By Cyrus Garnsey

NECESSITY FOR PRICE FIXING DURING the latter part of 1916 and the early months of 1917, clue to war activities, there was a threatened shortage of coal which resulted in panic among consumers and a rush to obtain coal at once at any price. As a result of this insistent demand for immediate delivery, prices were bid up by the consumers to unprecedented heights; spot coal which had previously been selling at from $1.50 to 82 per ton was bid up to $5, $6, and, in exceptional cases, as high as $7.50 or more per ton. Then when the April, 1917, contract period arrived, contracts could be made only at prices ranging from $3 up to $5 and $6 per ton for the year's delivery. This condition caused such a demoralization of the business, and so much complaint, that some action to regulate prices was considered essential by the National Administration. LANE-PEABODY AGREEMENT In May, 1917, a committee under the chairmanship of F. S. Peabody, of Chicago, was appointed by the Council of National Defense, through Mr. Lane, to consider the whole question of bituminous coal. This committee, with the Secretary of the Interior, Mr. Lane, after numerous meetings and long negotiations with the operators throughout the country, announced on June 29 an agreement between the Committee and the producers, fixing a tentative maximum price for bituminous coal throughout the country at $3 per net ton f.o.b. mines, to which was added 25 c. for selling commission to wholesalers. This plan was based on the idea of fixing a maximum price, high enough to greatly-stimulate production, with the expectation that the laws of supply and demand would, with ample production, operate to maintain fair and just prices for coal throughout the country.

Jan 9, 1918

By H. H. Evinger, M. Muskat

Although the shooting of oil wells for the purpose of increasing production has been practiced since 1866, present-day shooting technique has been arrived at almost wholly by a process of trial and error. The difficulties attending either a theoretical analysis of the problem or an experimental attack become apparent when one actually embarks on a theoretical investigation or attempts to formulate an intelligent experimental program. The literature on the subject consists mainly of descriptions of current practice, scattered eye-witness accounts of events following the shooting of a well, and vague speculations on the mechanical processes involved. In contrast to quarry blasting, the results of oil-well shooting cannot be determined by means of visual inspection, and it is perhaps for this reason that only one attempt at what approaches a direct experimental attack has been reported in the literature.' In these experiments, charges of liquid nitroglycerin were exploded in holes drilled in a sandstone outcrop. In order to observe the character and extent of the resulting fractures, the rock was blasted away so as to expose the original shot holes. After all this had been done it was found impossible to distinguish the fracturing due to the original shots from that due to the subsequent blasting. The enlargement of the holes due to the pulverizing action of the shots was measured and an attempt was made to determine the effectiveness if sand tamping. Only five shots were made and few definite conclusions could be drawn. Some small-scale experiments to deter-mine the effect of tamping were performed by Snelling and IIalL2 Small charges (zo grams) of dynamite were detonated at the bottom of a cylindrical hole in a lead block and the resulting enlargement of the hole was taken as a measure of the effectiveness of the explosion. It was found that when the shot was tamped with a sufficient amount of sand or clay, the volume enlargement was approximately double that found when no stemming had been used. The properties of the explosives have been the subject of much study by the manufacturers, the U. S. Bureau of Mines, and various other agencies. For example, velocities of detonation for many commercial explosives are to be found in the Blasters' Handbook, issued by the Du Pont company. Many other properties are given in a treatise on the subject by Naoum.~ The shock wave that accompanies the detonation of high explosives has been studied photographically by Payman4 and others. The hydrodynamical theory of the shock wave has received much attention, and an extended theoretical treatment is given by Bateman.6 Two aspects of the well-shooting problem will be considered in this paper; namely, the fracturing of subsurface strata, and possible damage to casing. With respect to the former of these, several calculations have been made giving the stresses in the rocks surrounding the shot. In order to arrive at numerical results at all, however, it is necessary to introduce a great many simplifying

Jan 1, 1941

By M. Muskat, H. H. Evinger

Although the shooting of oil wells for the purpose of increasing production has been practiced since 1866, present-day shooting technique has been arrived at almost wholly by a process of trial and error. The difficulties attending either a theoretical analysis of the problem or an experimental attack become apparent when one actually embarks on a theoretical investigation or attempts to formulate an intelligent experimental program. The literature on the subject consists mainly of descriptions of current practice, scattered eye-witness accounts of events following the shooting of a well, and vague speculations on the mechanical processes involved. In contrast to quarry blasting, the results of oil-well shooting cannot be determined by means of visual inspection, and it is perhaps for this reason that only one attempt at what approaches a direct experimental attack has been reported in the literature.' In these experiments, charges of liquid nitroglycerin were exploded in holes drilled in a sandstone outcrop. In order to observe the character and extent of the resulting fractures, the rock was blasted away so as to expose the original shot holes. After all this had been done it was found impossible to distinguish the fracturing due to the original shots from that due to the subsequent blasting. The enlargement of the holes due to the pulverizing action of the shots was measured and an attempt was made to determine the effectiveness if sand tamping. Only five shots were made and few definite conclusions could be drawn. Some small-scale experiments to deter-mine the effect of tamping were performed by Snelling and IIalL2 Small charges (zo grams) of dynamite were detonated at the bottom of a cylindrical hole in a lead block and the resulting enlargement of the hole was taken as a measure of the effectiveness of the explosion. It was found that when the shot was tamped with a sufficient amount of sand or clay, the volume enlargement was approximately double that found when no stemming had been used. The properties of the explosives have been the subject of much study by the manufacturers, the U. S. Bureau of Mines, and various other agencies. For example, velocities of detonation for many commercial explosives are to be found in the Blasters' Handbook, issued by the Du Pont company. Many other properties are given in a treatise on the subject by Naoum.~ The shock wave that accompanies the detonation of high explosives has been studied photographically by Payman4 and others. The hydrodynamical theory of the shock wave has received much attention, and an extended theoretical treatment is given by Bateman.6 Two aspects of the well-shooting problem will be considered in this paper; namely, the fracturing of subsurface strata, and possible damage to casing. With respect to the former of these, several calculations have been made giving the stresses in the rocks surrounding the shot. In order to arrive at numerical results at all, however, it is necessary to introduce a great many simplifying

Jan 1, 1941

By T. J. Woods

This paper deals with the origin, definition and prevention of scabs on semifinished rolled-steel product. Mold coatings, which are considered essential in scab prevention, were found to be effective only in relation to the ingot surface of semikilled and killed steels and not necessary for the rolled product. That is to say, the scabs on ingots caused by having been cast in uncoated molds are eliminated in the soaking and rolling operations, therefore are not present on the rolled product. This fact, which is contrary to the average opinion, was established after extensive and thorough experiments had proved the ordinary conception of the origin of scabs to be incorrect. This subject may be of little or no concern to steel plants producing small ingots for the manufacture of small billets and bars, except as it may be of interest in showing why their surface troubles with scabs do not exist on the product of heats with normal pouring practice. But to the producer of large ingots to be rolled into slabs for large plates used in shipbuilding, it is a very important subject. Definition of a Scab The generally accepted opinion is that the individual scabs present on rolled products (as shown by Fig. I) are considered to have been individual splashes on the ingot surface. This opinion was found to be incorrect. Experiments showed that there were no individual scabs on the product that had appeared as individuals on the ingot surface. The single scabs seen are either pieces of a shell that is present near the bottom of all top-cast ingots, or a veneer that may be present on any part of an ingot improperly poured, as when the stream strikes the mold wall. This definition is based on a detailed study of scabs and their characteristics in which the following have been found true: Location.—On the product of heats poured without trouble, scabs, if present, are always on the product that corresponds to the bottom end of the ingot, and usually occur in clusters. This is true whether molds are coated or not. Shape.—There is no regularity as to shape, size or thickness. It is sometimes possible to separate a few pieces and place them together, like pieces of a jigsaw puzzle, indicating that at one time they had been united as one piece. If individual splashes were the origin of scabs, the foregoing would not be true. Instead, the splashes, which occur throughout the pouring of the ingots, would be present uniformly over the entire product and there would be considerable similarity in the shape and thickness of the scabs. Experimental Work Our experimental work was conducted on 200-ton heats of semikilled plate steel tapped into an oval ladle 15 ft. high. All ingots were top-cast direct into 24 by 54 by 82-in. molds, straight-sided, set on flat stools. Two separate studies were made about one year apart, each study extending

Jan 1, 1943

By T. J. Woods

This paper deals with the origin, definition and prevention of scabs on semifinished rolled-steel product. Mold coatings, which are considered essential in scab prevention, were found to be effective only in relation to the ingot surface of semikilled and killed steels and not necessary for the rolled product. That is to say, the scabs on ingots caused by having been cast in uncoated molds are eliminated in the soaking and rolling operations, therefore are not present on the rolled product. This fact, which is contrary to the average opinion, was established after extensive and thorough experiments had proved the ordinary conception of the origin of scabs to be incorrect. This subject may be of little or no concern to steel plants producing small ingots for the manufacture of small billets and bars, except as it may be of interest in showing why their surface troubles with scabs do not exist on the product of heats with normal pouring practice. But to the producer of large ingots to be rolled into slabs for large plates used in shipbuilding, it is a very important subject. Definition of a Scab The generally accepted opinion is that the individual scabs present on rolled products (as shown by Fig. I) are considered to have been individual splashes on the ingot surface. This opinion was found to be incorrect. Experiments showed that there were no individual scabs on the product that had appeared as individuals on the ingot surface. The single scabs seen are either pieces of a shell that is present near the bottom of all top-cast ingots, or a veneer that may be present on any part of an ingot improperly poured, as when the stream strikes the mold wall. This definition is based on a detailed study of scabs and their characteristics in which the following have been found true: Location.—On the product of heats poured without trouble, scabs, if present, are always on the product that corresponds to the bottom end of the ingot, and usually occur in clusters. This is true whether molds are coated or not. Shape.—There is no regularity as to shape, size or thickness. It is sometimes possible to separate a few pieces and place them together, like pieces of a jigsaw puzzle, indicating that at one time they had been united as one piece. If individual splashes were the origin of scabs, the foregoing would not be true. Instead, the splashes, which occur throughout the pouring of the ingots, would be present uniformly over the entire product and there would be considerable similarity in the shape and thickness of the scabs. Experimental Work Our experimental work was conducted on 200-ton heats of semikilled plate steel tapped into an oval ladle 15 ft. high. All ingots were top-cast direct into 24 by 54 by 82-in. molds, straight-sided, set on flat stools. Two separate studies were made about one year apart, each study extending

Jan 1, 1943

Present indications are that the Fourth National Exposition of Chemical Industries, to be held in Grand Central Palace, New York, Sept. 23 to 28, will be the greatest exhibition of its kind ever held. Preparations are well under way and the advisory committee is working hard to make, every department of the affair a success. Men prominent in the chemical and allied industries will speak on subjects vital to present conditions and needs. Dr. C. H. Herty, and Dr. G. W. Thompson, President of the American Institute of Chemical Engineers, are to make opening addresses. F. J. Tone, President of the American Electrochemical Society; Dr. W. H. Nichols, President of the American Chemical Society, and several others, are expected to make addresses also. Prof. Joseph W. Richards will speak on : ?Ferro-alloys of silicon, tungsten, uranium, vanadium, molybdenum, and titanium." Theodore Swann, President of the Southern Manganese Corporation will speak on "Ferro-manganese." The program for the exposition is in active preparation. There will be a series of symposiums on the "Development of Chemical Industries in the United States, notably since July, 1914." Among other topics for consideration is that of potash development; C. A. Higgins, of the Hercules Powder Company, will speak of the operations of that company in the recovery of potash from kelp; Linn Bradley, of the Research Corporation, on its recovery from cement dust, and other sources, by electrical precipitation. Other symposiums will be devoted to chemical engineering, acids, industrial organic chemistry, the ceramic industries, and the metal industries. Among the speakers are: A. Hough.-" Chemical Engineering in Explosives: TNT; TNA; Picric Acid; and Nitrobenzol." E. J. Pranke.-" Development of Nitric Acid Manufacture." S. P. Sadtler.-"Development of Industrial Organic Chemistry." Geo. H. Tomlinson.-" Wood as a Source of Ethyl Alcohol." C. A. Higgins.-"Kelp as a, Source of Organic Solvents." Alcan Hirsch.-" Pyrophoric Alloys."

Jan 9, 1918

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By R. M. Brick, Arthur Phillips

The Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic problems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segregation. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute concentration, with a resultant normal segregation or coring effect during freezing. Theoretically, musion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions aluminum-copper alloys segregate inversely and aluminum-magnesium alloys segregate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944