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COMMITTEES Committee on Arrangements DAVID H. BROWNE, Chairman BRADLEY STOUGHTON, Vice-Chairman LAWRENCE ADDICKS BURR A. ROBINSON PERCY E. BARBOUR E. MALTBY SHIPP GEORGE D. BARRON JOSEPH STRUTHERS J. V. N.. DORR E. B. STURGIS J. R.. FINLAY T. T. READ Louis D. HUNTOON R. H. VAIL

Jan 4, 1916

By Raymond C. Boettner

The present work had for its purpose: 1) the identification of crack nucleation sites in AISI 4340, quenched to martensite and tempered over a range of 'temperatures; and 2) the comparison of fatigue processes in AISI 4340 with processes observed previously in pure metals From constant def1ection-bending fatigue tests, martensite boundaries were identified as the favored crack nucleation sites in quenched and tempered AISI 4340. It, also, was concluded that the fatigue processes operating- in this lous-alloy steel were similar to Processes observed in pure tnetals. ALTHOUGH much engineering data has been accumulated on the fatigue properties of quenched and tempered martensitic steels,' fatigue as a process is not as well understood in martensite as it is in pure metals.' Important features of the fatigue process, such as the identity of the nucleation sites, have not been determined in the commercially important high-strength low-alloy structural steels. The present work had for its purpose: 1) the identification of crack nucleation sites in a low-alloy steel, i.e., AISI 4340, which had been quenched to martensite and tempered over a range of temperatures; and 2) the comparison of fatigue processes in the AISI 4340 with processes observed previously in pure metals. This comparison of the fatigue processes in the different tempers was restricted to the high-strain low-cycle part of the S-N curve. Under these test conditions, previous work on a number of metals has shown that a large number of cracks are nucleated in less than 30 pct of the fatigue life.3 Furthermore, crack nucleation sites are not restricted to inclusions but are also associated with intrinsic structural characteristics of the metal. MATERIAL A 20-lb ingot of vacuum-melted AISI 4340 (for composition see Table I) was hot-rolled to 1-in.-diam rod and then cold-rolled to a 1-in.-wide strip, 0.08 in. thick. Fatigue specimens, see insert of Fig. 1, were machined from the strip with the long dimension parallel to the rolling direction. m this orientation, the stringers of 1 to 2 p inclusions present in the sheet lay parallel to the stress axis in the specimens. The specimens were austenitited at 2050°F in order to obtain a large prior austenite grain size, i.e., 2 mm, which facilitated the subsequent identification of the prior austenite boundaries. A helium atmosphere was used to minimize decarburization. After austenitiza-tion at 2050°F, the specimens were transferred to a 1450°F furnace so that specimen distortion was held to a minimum in the subsequent oil quench. Previous work4 indicated that refrigeration in liquid nitrogen prior to tempering reduced the percentage of retained austenite in the quenched specimens to less than 5 pct. Tempering was carried out in air over the temperature interval of 200°to 800°F to produce a range of mechanical properties, Table I. The preparation of the fatigue specimen was completed by grinding about 0.005 in. from each surface and electropolishing in a chrome trioxide-acetic acid solution for 30 min. Examination of etched cross sections of specimens prepared in this fashion showed the foregoing specimen preparation to be adequate for the removal of the decarburized layer present after the heat treatment. Transmission electron microscopy showed that the as-quenched microstructure of this alloy consisted of a mixture of martensite plates containing either a high density of dislocations or microtwins. Previous work5'6 indicated that in the course of oil quenching autotem-pering resulted in the formation of E carbide on the martensite and microtwin boundaries. Tempering for 2 hr at temperatures up to about 400°F resulted in further precipitation of the E carbide. Finally, at about 400°F, cementite began to replace the E carbide on the martensite and microtwin boundaries in addition to forming a Widmanstatten structure within the plate matrix. EXPERIMENTAL S-N curves were obtained using electropolished specimens cycled at 1800 cpm as cantilever beams in fully reversed bending at selected constant deflections. The deflections were translated into surface strains by means of a calibration curve obtained through the use of strain gages. An argon atmosphere was used to minimize environmental effects. To investigate the development of fatigue slip bands, the specimens of the different tempers were unidirec-tionally bent to a surface strain of 0.005 to 0.007, photographed to record the location and appearance of slip bands so introduced, and then cycled to failure

Jan 1, 1968

By A. H. Jones, J Leasia, S. J. Green, R. D. Perkins

Previously, two groups have conducted studies in order to define the influences of the intermediate principal stress. Mogi studied biaxial compression on prisms of Dunham dolomite and concluded that the intermediate principal stress should be taken into account. His study showed that failure strength increases with increasing [02], but less than the strength increase with increasing confining pressure. Handin, Heard, and Mogouirk's study on cylinders of Solenhofen limestone in torsion also found that the strength depends on the magnitude of [02]. More recent investigations by Mogi varying all three principal stresses independently and by Wawersik varying two of the principal stresses independently provide more detailed data confirming the effect of [02] on failure. All these tests were at low strain rates, and only the work of Wawersik reports measurement of all strains. The investigation here measures axial and transverse strains and included uniaxial and triaxial stress compression tests and biaxial stress tests using tubular samples (axial load and internal or external fluid pressure) at strain rates to 103/sec to provide the stress-strain response and to define the maximum stress or yield locus of Solenhofen limestone and Westerly granite.

Jan 1, 1971

By Grover J. Holt

A DETAILED description of the many variations in iron mining and transportation practice in Minnesota would require much space. Since a fairly detailed description of the practices then in use was published in the guidebook issued in connection with the meeting of the Institute on the iron ranges in I920, and subsequent developments have been described by E. E. Hunner,1 M. H. Barber,2 and A. E. Anderson, J. M. Riddell and G. J. Holt,3 it will not be necessary here to do more than review the highlights of current practice. Details on any points of interest can be obtained through correspondence with the operators involved. [T] The iron ores of Minnesota, which have been formed through enrichment of the iron formation in which they occur, largely by the removal of silica, are usually covered by a blanket of glacial drift known locally as "surface." Surface material, including sand, clay, hardpan and boulders, makes up the greater portion of the stripping in open-pit operations. In some instances, stripping also includes taconite and "paint rock," directly below the surface material and overlying the ore. Taconite is the iron formation, a ferruginous chert with interbedded slate layers. "Paint rock" is a local term for oxidized slate layers interbedded in the iron formation, high in phosphorus, alumina and moisture. The iron ores fall into two classes: (I) direct shipping (merchantable ores or ores requiring no treatment except possibly crushing or screening to make an acceptable sized product), and (2) ores requiring beneficiation (such as sintering, drying, washing, jigging, high-density treatment, or magnetic separation in the case of magnetite). The Mesabi Range produces chiefly soft Bessemer and non-Bessemer ores. The Cuyuna Range produces mainly low-manganese brown ore and high-manganese black ores, with some iron ore. The Vermilion Range yields mainly Besse¬mer and non-Bessemer iron ore, with some hard or lump ore that finds use in the open hearth. Open-pit mining is limited to the Mesabi and Cuyuna Ranges but underground mining is done on all three. The choice of mining methods is determined by the relative economics of overburden¬-removal and shaft-mining costs. STRIPPING PRACTICE Common practice has been to remove the bulk of the overburden during the winter season and to mine during the summer. In the present emergency many operators are forced to forego the economies attained by year-round utilization of equipment and to equip for, and carry on, stripping and mining simultaneously. In the normal years or lean years to come, most properties probably will be over-equipped and high depreciation charges will have to be absorbed.

Jan 1, 1942

By F. F. Poland

The purpose of this paper is to describe the recent applications and improvements made in the process and equipment for the recovery of metallic zinc from secondary metals by means of high temperature electric resistor furnace distillation. The process and high temperature furnace, as developed by Revere Copper and Brass Incorporated, Research and Development Department, was described in a previous paper. † Since the publication of that paper the process and equipment have been licensed to others. Consequently its field of application has been expanded, particularly for the treatment of scrap brass, galvanizers dross and scrap zinc. Other applications are being considered, particularly the melting of metallic titanium and special alloys requiring a controlled atmosphere. Consideration is also being given to modification in design that would allow the melting of copper cathodes for the production of oxygen-free and electrolytic tough pitch copper shapes without the necessity of blowing and poling. In the design of a furnace for melting copper cathodes it is intended that the fundamental principle of charging the solid material into a large pool of molten metal through a double door charging vestibule as shown in Fig 3 of the previous paper, † would be adhered to and, in addition, either dehydrated and desulphurized producer gas or commercial nitrogen, that is, approximately 96 pct nitrogen, 2 pct hydrogen 2 pct CO, also dehydrated, would be used to provide a protective atmosphere for the resistors and to flush out more soluble gases from the molten copper. The operation of a small unit producing approximately 1000 lb of copper per hr has shown that the commercial nitrogen will allow the production of tough pitch electrolytic copper when the metal is transferred from the meltdown unit contemplated to a special type induction unit where the oxygen absorption and temperature can be controlled. Standard practice in treating low grade scrap brass has been to oxidize the zinc by blowing air through the molten metal. This operation results in the recovery of approximately two-thirds or less of the zinc content of the brass in the form of an impure zinc oxide having only a fraction of the value of the zinc in metallic form. The balance of the zinc is lost to slag, fume and drosses. Fig 1 shows the revised flow sheet of the process for the treatment of scrap brass. For this application and as shown on the flow sheet a low frequency induction furnace has been substituted for the Wilkins-Poland type as a melting unit. This type of furnace has been found the most suitable for the purpose as will be shown by the following discussion. Serap Brass The melting of refinery scrap brass preparatory to distillation presents a melting problem quite different from the usual melting of brass mill scrap for recasting because refinery scrap is a heterogeneous mixture of alloys each having different melting and boiling points, and coated with a variety of corrosion products and foreign materials. In addition, brass and copper plated pieces of sheet iron, stainless steel, ceramic materials, and others are present that do not melt except at temperatures above the boiling point of the liquid bath. In the previous paper it is noted that difficulty was encountered in the melting of refinery grade scrap brass without excessive loss of zinc by volatilization and that 5 to 10 pct razorite flux was used to alleviate this condition. While this flux was successful in preventing the excessive loss of zinc by volatilization it interposed a low heat conductivity layer between the source of heat and liquid charge and resulted in lowering the melting rate of the furnace. This same problem presents itself in all types of furnaces in which the metal is heated by radiation and conduction from above the charge. It has been found in melting this type material that the melting rate per hour or per square foot of hearth area

Jan 1, 1950

By W. C. Lilliendahl, H. W. Highriter

The method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon completion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then prcssed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times tile uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphitc crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of CO² in Ascarite, using air instead of oxygen to reduce the temperaturc and rate of oxidation. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1). Microscopic examination of ductile and brittle metals disclosed the presence in the latter of an intergranular constituent, harder than the matrix and less easily oxidizable, which was absent from the ductile material. Rough estimates of the volume of the hard constituent

Jan 1, 1935

By W. C. Lilliendahl, H. W. Highriter

The method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon completion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then prcssed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times tile uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphitc crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of CO² in Ascarite, using air instead of oxygen to reduce the temperaturc and rate of oxidation. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1). Microscopic examination of ductile and brittle metals disclosed the presence in the latter of an intergranular constituent, harder than the matrix and less easily oxidizable, which was absent from the ductile material. Rough estimates of the volume of the hard constituent

Jan 1, 1935

By J. W. Spretnak, G. W. Cunningham

Grain growth across the bond region in Pressure bonded copper was found to be mainly dependent upon the presence or absence of microvoids, but it was also found that prior history, bonding pressure, bonding time, and bonding temperature are important variables. An increase in pressure, time, or temperature tends to promote grain growth in the interfacial region. Polygonization is observed after pressure bonding except for specimens previously annealed at temperatures on the order of 1800°F or higher. The dislocation density in bonded specimens was found to be greater in the bond region. THE bonding of metals by the application of gas pressure at elevated temperatures is a relatively new process, having been developed over the past 10 years. The technique, as described by Paprocki, Hodge, and Boyer,l is unique in that assemblies of many parts and complex shapes can be bonded with a negligible amount of deformation. The process thus differs metallurgically from pressure welding, cold welding, and recrystallization welding in that deformation occurs only in a microscopic region whereas, in general, the welding requires severe deformation and may extend the contact surface by a factor of 3 to 10 during the welding. From a practical standpoint, pressure welding is not amenable for bonding large surfaces. During the time in which Paprocki and coworkers were deve1oping the process, West2 established aproc-ess,for bonding aluminum to uranium, and Barnes and Maze? developed a gas-pressure-bonding technique for nickel and copper. Recently, Fugardi and Zambro4 have used equipment similar to that developed by Paprocki and coworkers to establish parameters for bonding stainless steel, aluminum, and zirconium. Most of the investigations on pressure bonding have been empirical in nature and, although methods have been developed for bonding such metals as molybdenum, columbium, titanium, zirconium, and stainless steel, the information concerning the mechanism of bonding is limited. Several workers5"7 have studied the pressure bonding of dissimilar metals in order to gain information on diffusion and formation of inter-metallic phases under application of pressure. Clapson and Robbins8 have shown by a series of annealing studies that voids in the interfacial boundary of roll-bonded copper can prevent movement of the boundary until the voids are spaced far enough apart to prevent pinning. They also indicated that recrystallization and grain growth can eliminate the voids. In this paper it is shown that voids are the major detriment to grain growth across pressure-bonded interfaces, but it is also shown that prior history, bonding pressure, bonding time, and bonding temperature are

Jan 1, 1962

By A. M. Gaudin

TEN years ago Taggart, Taylor and Ince1 described a workable, convenient apparatus for the measurement of contact angles be-tween cleaved, ground or polished particles and captive bubbles. Wark and Cox2 and Wark and Sutherland3 have done an im-mense amount of experimental work with this apparatus. Their work has had as principal object the determination of "con-tact curves." Contact curves are Cartesian charts in which pH (or some other variable) is plot-ted against quantity of modifying agent. The rectangular area is broken into two or more curvilinear areas separated by the contact curve. The curve indicates that a sharp demarcation exists between condi-tions that bring about sticking of particles to bubbles and conditions that do not pro-duce sticking, The type curve appears in the TRANSACTIONS as Fig. 1, page 248, volume 112. Wark and Cox offer data to show that the contact angle has a value determined by and characteristic of the agent used. Wark and Cox also make the statement that they believe this value is independent of concen-tration (ref. 2a, p. 209), They say: It is suspected that, given sufficient time and provided that there are no disturbing factors. the full ethyl xanthate angle (corresponding to a complete xanthate film) would be obtained in every case where contact occurs.

Jan 1, 1940

By J. W. Lewis

This review covers that portion of the area between the Llano mountains and the Red River which lies between Fort Worth and Abilene. The counties and fields included are listed in Tables 1 and 2. During 1929 there was a marked lull in both prospecting and development in this part of Texas. Archer, Coleman, Cooke, Wilbarger and Young were the counties most active. The total gross production of the year was 52,611,000 bbl., 3 per cent. more than for 1928. The production of the Coleman, Cooke-

Jan 1, 1930

By Kenneth C. Vincent, A. M. Gaudin

TEN years ago Taggart, Taylor and Ince1 described a workable, convenient apparatus for the measurement of contact angles between cleaved, ground or polished particles and captive bubbles. Wark and Cox2 and Wark and Sutherland3 have done an immense amount of experimental work with this apparatus. Their work has had as principal object the determination of "contact curves." Contact curves are cartesian charts in which pH (or some other variable) is plotted against quantity of modifying agent. The rectangular area is broken into two or more curvilinear areas separated by the contact curve. The curve indicates that a sharp demarcation exists between conditions that bring about sticking of particles to bubbles and conditions that do not produce sticking. The type curve appears in the TRANSACTIONS as Fig. 1, page 248, volume 112. Wark and Cox offer data to show that the contact angle has a value determined by and characteristic of the agent used. Wark and Cox also make the statement that they believe this value is independent of concentration (ref. 2a, p. 209). They say: It is suspected that, given sufficient time and provided that there are no disturbing factors, the full ethyl xanthate angle (corresponding to a complete xanthate film) would be obtained in every case where contact occurs. Such a conclusion, if correct, would tend to substantiate the hypothesis of flotation collection by metathesis championed by Taggart and his associates4-8 and would argue against the adsorption hypothesis now adopted by Wark7 and by one of us.8 However, the data of Wark and Cox do not bear out the conclusion that there is a sharp passage from conditions of contact to conditions of noncontact. Rather, they indicate the existence of a transition zone of reagent concentration across which the contact angle varies with changes in reagent concentration from zero to a value near the maximum. This may be seen, for example, from Fig. 195 in the new text by one of us (ref. 8, p. 380), which presents the data of Wark and Cox in graphical form. The object of this study has been to explore the nature of the transition from conditions of contact to conditions of noncontact. The data of Wark and Cox to which reference has been made as showing that a gradual transition exists are marred by the fact that the region of critical-agent concentration is at an extremely small concentration. This condition suggests that diffusion may have played such a preponderant role that equilibrium was not reached within the time alloted. In the Wark and Cox data, the critical concentration was at about one part of xanthate per million parts of water. To form a monolayer of xanthate on the mineral surface would therefore require depletion of xanthate in the liquid to a depth of the order of

Jan 1, 1940

By J. B. Seabrook

The accompanying Fig 1 is a graphical scheme of intermediate accuracy for expediting interconversions of mol, weight, and volume percents. This chart consists of a family of curves of mol or atomic or volume percent plotted against weight percent, each curve in the family providing for a certain ratio of molecular or atomic weights or densities. Thus, the whole range of variations is presented in a very familiar format, and the conversion is effected simply by choosing the proper curve and reading off the required values. An entire series of conversions for a given binary system can be found by following the appropriate curve. It is interesting to examine the analytical geometry of the plots. The curves, which must fit into a square and all join at the 0 and 100 pet points, may be shown to be hyperbolas with their centers on the extension of the diagonal of the square which they intersect. Multiplying out the expression x A atomic fraction of A = y = ------ where x is the weight fraction of A, and A and B are atomic weights, we get xy+A/By- A/Bxy=x Upon rotating and translating axes and avoiding imaginaries, it is found that the angle of rotation is —45°, the origin moves upv2/2 units andv2/2(A/B+1/A/B-1) units to the right, and the standard form is Thus the curves are equilateral hyperbolas, their centers are units away from their intersection with

Jan 1, 1950

By A. L. Holley

THE occurrence of this gas, in quite appreciable. quantities, has been observed for many years in its escape along the creeks of Western Pennsylvania, and more recently, in much larger quantities, from the oil wells in and near Venango County. Within about five years several gas wells have been struck, from which the gas has escaped continuously in prodigious quantities and at great pressure. During the last year a systematic attempt has been made to utilize the flow of gas from one of these wells, and results have been reached which were quite unexpected. This well, near Leechburg, Armstrong County, is about twenty miles northeast of Pittsburgh, on one of the side tributaries of the Alleghany River. It had been drilled in search of oil to a depth of 1250 feet in 1871, but none was found. A great flow of gas was developed, however, accompanied by a slight spray of salt water, and this has continued with little or no diminution to the present time. The gas in its escape has been discharged through a 5-inch pipe, and at a pressure of from 60 to 80 lbs. per square inch, but no exact determinations, either of the pressure or quantity, have been made. The rolling mill of Messrs. Rogers & Burchfield is on the opposite side of the river, and it has been for some years devoted to the production of fine grades of sheet iron from charcoal pig metal, by puddling and in knobbling fires. The usual weekly product of the mill has been 30 tons of No. 30 tin plates, and 50 tons of No. 24 to 28 sheets. The well was bought by this firm for $1000, and the gas is led across the river, a distance of about 500 feet, through a 3-inch pipe. It is distributed through half-inch pipes, and at a pressure of about 45 lbs. per square inch, to several of the furnaces, but a large fraction of the total flow of gas is still wasted at the well. No essential alteration in any of the furnaces has been found necessary in the use of the gas fuel, except to brick up the fire-bridge and to put in the gas and air pipes. The old grate used for coal is loosely covered with bricks and cinder, so that a slight percolation of air may take place through them. The gas is admitted through a half-inch pipe, and blows toward the fire-bridge through 18 or 20 one-eighth inch jets. The air is blown in at about 2 lbs. a

Jan 1, 1876

By Jerry B. Newby

The outstanding features in Pennsylvania and New York during the past year were the buying of acreage for water-flooding in other Pennsylyania fields than the Bradford and Allegany districts, the wide adoption and use of the five-spot plan of development and water-flooding in the Bradford and Allegany districts, the discovery of gas production in the Onondaga lime in southwestern New York and the opening of the T. W. Phillips Gas & Oil Co. Fifth Sand pool in Butler County, Pennsylvania. Water-flooding has occurred in many other fields than the Bradford, Pa., and Allegany, N. Y., fields. In some the flood was a natural encroachment of edge water, in others the water was introduced into the productive sand through wells either accidentally or intentionally. Most of these floods have not been commercially successful. There has been some interest aroused in the Clarendon field, Warren County, Pennsylvania, by a new and apparently successful flood and other floods have been begun. Five-spotting in the Bradford and Allegany fields is the plan of water-flood development under which the area to be drilled is laid off in a grid of equal-sized squares with water intakes located at each corner of the squares and oil wells located in the centers of the squares. So far there are two five-spot water floods that are, beyond doubt,, commercial successes. There were 600 acres under five-spot flooding at the end of 1928, as against 150 at the end of 1927. By the end of 1929 there will be a total of between 1200 and 1500 acres five-spotted unless a low market for Pennsylvania grade crude oil develops. An increase of 6000 bbl. in average daily production is expected to accompany this development in 1929. The Belmont-Quadrangle Drilling Corpn. found the Onondaga lime or a higher strata at 3995 ft. north of Bolivar, Cattaraugus Country, N. Y., and a number of miles from any other important gas production. When drilled to 4006 ft. the well yielded 3,500,000 cu. ft. of gas and when shut in 1700 Ib. rock pressure. The one oil pool opened in 1928 was in Buffalo township, Butler County, Pa., in October, when the T. W. Phillips Gas & Oil Co. completed a wildcat well in the Fifth sand at 700 bbl. a day, which by the end of

Jan 1, 1929

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By M. C. Messner, L. P. Davidson

The Giesche Spas Akcyjna, in Polish Upper Silesia, produces zinc, lead and coal, together with many byproducts emanating from the zinc-lead ores. The development of the concern in the 230 years of its existence has been influenced not only by metallurgical improvements but also to an unusual extent by political and economic factors. The company was founded by George Giesche, who was born in 1653 and died in 1716, and who in 1704 received from Emperor Leopold I the exclusive privilege of mining and selling galmei1 in Silesia. His children, who retained the business, gave the name to the firm—George von Giesches Erben. After 1802 modifications in the Prussian mining and corporation laws limited the rights formerly enjoyed. The family concern became a corporation and expanded its activities, building smelters and opening new mines. The establishment of the present eastern boundary of Germany resulted in the transfer of nationality of a large part of the mines and surface plants to Poland, which, in turn, necessitated the formation of a Polish company, the Giesche Spólka Akcyjna. The first concentrators at the Bleischarley mine were built between 1854 and 1860 and owing to dual ownership were two in number. They were used only for the treatment of galena. In 1873 a concentrator was built for the treatment of sulfide ore preparatory to treatment in the Recke roasting plant, which was the first to have an acid plant for recovery of the sulfur gas. This concentrator was replaccd by a larger one in 1888, when the present orebody was opened up. At the same time, a mill was built for the treatment of the galmei. The concentration of the sulfide ore resulted in a much higher grade of feed for the zinc plants after the first troublesome steps of the roasting process had been worked out. Consequently, the oxide ore in its primitively concentrated state was no longer highly valued as a retort charge. and steps had to be taken to increase its zinc content.

Jan 1, 1935

By Frank Firmstone

In the Kaernthner Zeitschrift, No. 2, 1881, p. 53, et seq., Prof. Ledebur details some experiments on the power of various silicates of lime and alumina, magnesia and alumina, and lime, magnesia and alumina, to remove sulphur from pig-iron, from which it appears (as has long been recognized in practice) that the more basic the silicate the greater the quantity of sulphur it will take up; but also that for the same grade of silicate, this quantity is greatest for the lime-alumina silicate and least for the magnesia-alumina silicate, the lime-magnesia-alumina silicate occupying an intermediate position, and he concluded therefrom (p. 59) that, for the production of pig-iron low in sulphur, pure limestones are to be preferred to those containing magnesia. Much the same opinion has been published elsewhere on high authority, and lately (not to multiply references) by Sir Lowthian

Jan 1, 1895

By H. E. Wrigley

The boundaries of the oil region in Pennsylvania and New York, as determined by the drill, embrace a much larger extent of territory than is generally supposed, being nearly 200 miles in length from north to south, with an average width of 25 miles, covering an area, within somewhat irregular lines, of about 4250 square miles. After twenty years of development we find these lines practically the same as those laid down by McClure in his geological map of the United States, published in 1817, and denominated and colored by him as the "line of salt," which was found in quantity long before petroleum. The eastern line of the entire oil region lies in a northeast and southwest direction, parallel to and some distance west of the Allegheny Mountains; the south line is substantially one drawn between the western boundary of Butler County and the town of Kittanning in Armstrong County; the west line passes just outside of Butler County, cutting off a small corner of Mercer, west of the towns of Franklin, Titusville, and Warren, into New York State, where it rounds off the end of this long strip in the counties of Allegheny and Cattarangus, and joins the eastern line, near Olean, New York, north of the city of Bradford. (See map.) The eastern line, starting from Kittanning, passes through the northeast corner of Clarion County, the southeast corner of Warren, cutting Forest County through the centre, and reaching the beforementioned extreme northeastern developments near Olean. These lines have been taken broadly to include all territory that could ever possibly come into the question as oil-producing. These lines having been proved by the drill may be considered

Jan 1, 1882

SAMUEL T. HOYT,? Minneapolis, Minn. (written discussion||).-The subject of grain inheritance in iron and steel is apparently one which can he considered from the point of view of the two laws governing the rate of formation of crystal nuclei and the linear velocity of crystallization, which have been investigated by Tammann and collaborators, and of the additional law of coalescence. According to the work of Tammann, both the nuclei number, which is taken to be the number of crystal nuclei to form per unit volume per unit time, and the linear velocity of crystalli-

Jan 5, 1918

By Thomas M. Drown

I DESIRE to communicate to the Institute the results of a few analyses which bear on the condition of carbon in gray and white iron. These analyses were made in the course of an investigation, now in progress, of the chemical composition of "chilling" irons. It will be remembered that Bell says he found no material difference in the amount and condition of carbon in gray and white pig iron made at the Clarence furnace, in England, and he therefore refers the difference in color and appearance in these two varieties of iron to the size of the particles of graphite. I quote from his "Chemical Phenomena of Iron Smelting:" "The inference I would draw from the information afforded by these analyses is, that the condition of iron in respect to its so-called 'richness' is, within certain limits, entirely independent of its chemical constitution.. .. In the fluid state, I conceive the carbon, so taken up, confers upon the iron the property of fusion much below the temperature at which the pure metal melts, and the carbon itself may be regarded as dissolved in the iron. If, during the process of manufacture, the pig metal has been formed at a low temperature, consolidation, I imagine, takes place under such circumstances that the crystals are so minute, and the carbon which is separated assumes the uncombined or graphitic form in particles so minute as to be invisible, and, in consequence, the iron is white. If, on the other hand, the furnace is working at a very high temperature, the intensely heated iron crystallizes with large facets, upon which the extruded carbon assumes the condition of distinct plates or flakes. Should the temperature be less intense, these crystals are of smaller dimensions, and the separated carbon is less conspicuous, and, as the temperature of the furnace declines, the crystals decrease in size, as do the flakes of carbon, until both disappear in white iron.. .. Returning, then, to temperature as the cause of differences in quality of pig iron, the 'chilling' of gray metal, and its conversion into white, may be regarded as the effect of preventing, by rapid cooling, the formation