Search Documents

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By P. R. Sperry, A. P. Beck

It has been shown1 that in poly-crystalline strips of high purity aluminum with a fairly random orientation distribution, grain growth progresses gradually until the average grain diameter reaches a value approximately equal to the strip thickness. Recent work at this laboratory led to the realization that grain growth might be impeded to a considerable extent in the presence of a sharply defined texture, where orientation differences between neighboring grains are small. In order to investigate this effect the following experiment was carried out with the same lot of high purity aluminum previously used for grain growth studies in randomly oriented material.' Very large grain size was developed by grain growth at 650°C in specimens of 0.200 in. thickness. These specimens were then rolled to a thickness of 0.050 in. or 1.25 mm—a reduction of 75 pct. In the rolled strip each large grain corresponded to an elongated area easily identified by etching. After annealing for 1 to 25 min at 600°C and re-etching, these elongated areas were again recognizable. Within each area, corresponding to a single large grain before annealing, there formed by recrystallization a multitude of new grains with a fairly well developed preferred orientation. The orientation and the size of the new grains formed in areas corresponding to different large grains, varied widely depending on the orientation of the parent grains with respect to the rolling direction and the plane of rolling. Many areas were found where the average grain size was considerably smaller than the specimen thickness. Such an area occurred in a specimen cut in half before annealing. One half, containing a portion of the area in question, was annealed 1 min at 600°C, the other half, with the remaining portion of this area, for 25 min at the same tempera-Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950

• A new curriculum for combined liberal arts-engineering education has been announced by 6 middle western colleges. The plan involves three years of ;study at one of the 5 liberal arts colleges and two years and a summer of 'engineering work at Case; graduates receive both the A.B. and B.S. degrees. * A new kind of mining is being pioneered by a pest Virginia coal operator which enables four men to produce 800 tons of coal a day. The machine that makes this possible is a giant auger, 5 ft in diam and 100 ft long. Together with the carriage in which it is moved about, it weighs 60 tons. A mobile, but separate power plant of 1000 hp drives it. ' * The Sorel smelter, which will reduce Allard Lake titanium ores, will utilize five 6-electrode rectangular electric furnaces. Furnace hearth size will be about 18x50 ft, and the furnace will smelt about 300 tons of ore per day, producing 100 tons of iron and 130 tons of 70 pct Ti02 slag. The furnaces will be fed continuously by gravity from charge bins, and tap at intervals of 4 hr or more. Slag will be transferred to a high speed casting machine, using cast iron molds, then crushed for shipment to pigment producers. The iron will be treated to reduce its sulphur content to 0.03 to 0.05 pct, and then cast into small pigs or ingots for shipment to steel mills. • Flying of North Africa's first airborne mangetometer survey was completed this month, covering approximately 20,000 sq km in north central Tunisia for Gulf Exploration Co.'s program there. Mapping was completed in less than 30 days. •Yore than 9000 employees of 11 electric companies are enrolled in a 6-hr program that successfully informs workers on the principles of the American economic system. The course is given by the Middle West Service Co. which claims that before and after employee opinion polls show that the course instilled a better understanding of free enterprise and consequently a favorable response to it. •According to a report issued by the American Geological Institute there will be 2865 graduates in geology, including advanced degrees from U.S. colleges in 1950. This supply of geologists compares with requirements for 1278 at the professional and subprofessional levels. The report contains a detailed statistical study of the supply and demand situation for geologists in the 1949-50 period. •The dark cloud of over-production in the bituminous coal industry has a silver lining, according to Natural Resources Notes. Closing marginal mines, mostly strip and truck mines, will result in lower average costs and higher quality of the coal still produced. The producers that will then constitute the industry will be properly equipped and adequately financed to carry forward an intensive campaign to holdd and increase the markets for bituminous coal. •A light, compact, highly reliable blasting machine which does not rely for its effectiveness on the operator's skill is being tested by the Army Engineers. Operating under all climatic conditions from -65 to 125F, the 50-cap machine consists of a springwound do generator and is waterproof.

Jan 8, 1950

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

E. K. Landis, Philadelphia, Pa. (communication to the Secretary) : Mr. Firmstone's paper is of great interest; but he has unfortunately otnitted to state the most important point, viz., the percentage of sulphur in the two materials he compares; and this omission vitiates the conclusions which he draws. Comparing by grade, instead of silicon-contents (as in his Table III.), the iron made using limestone with that made using dolomite, we find for gray-forge the average of four analyses under limestone to be, Si, 0.644; S, 0.089 ; while one analysis under dolomite gives Si, 0.508 ; S, 0.070. For No. 2 iron, the limestone flux gives, as an average of 19 analyses, Si, 1.107; S, 0.051; while the average of 4 analyses made with dolomite flux gives Si, 0.630; S, 0.056. It will be observed, that no No. 1 pig is given under limestone, while 14 analyses appear under dolomite, averaging Si, 0.950 ; S, 0.028. As nothing is said about changed conditions, it is Fair to presume that the ore and fuel, as well as the blast-temperature (which is stated to have been uniform at about 750' F.) remained practically the same; and since the sulphur in the two fluxes is not given, it is impossible to know whether the lower sulphur for equal silicon-contents is due to the use of dolomite or to other conditions. The use of dolomite would produce a more fusible cinder, and the furnace would be hotter than when using limestone; therefore, we might expect to see a grayer iron. The amount of So. 1 iron made with dolomite seems to confirm this supposition; and, under these conditions, we might expect more of the sulphur to be volatilized, and to pass off in the gases. The easier fusibility of the cinder would also permit more rapid driving; and this should reduce the amount of silicon and sulphur in the iron, as the amount of reduced metalloids in the pig is directly proportional to the length of time it remains in the reducing-zone.

Jan 1, 1895

George Edward WebbeR, a member of the Institute since 1906, died in San Francisco, May 29,1922. Born in Dixmont, Me., in 1852, he went to California in 1857 where he lived until 1883 and received a thorough training in precious metal mining in the employ of his father and J. B. Haggin. In 1883, he went to the Black Hills, South Dakota, as superintendent of the Father DeSmit mine; later the Deadwood Terra also came under his management. These mines are now part of the Homestake Mining Co. In 1889, the Rothchilds asked Hamilton Smith to recommend an engineer to take the place of the late Henning Jennings, who had resigned from the El Calloo Mining Co., of El Calloo, Venezuela, in order that he might proceed to South Africa. Mr. Webber accepted the position, remaining there until 1893 when he returned to the United States on his way to Johannesburg, South Africa, where he had been appointed manager of the Crown Reef Mining Co., Ltd. Early in 1896, he became general manager of the Rand Mines, Ltd., and served in this capacity until 1911. During the latter part of this period, Mr. Webber was active in the greater amalgamations of H. Eckstein & Co., and it was largely on his advice that H. Eckstein & Co. carried out the negotiations preceding the formation of the Crown Mines, Ltd. On his retirement from South Africa, he returned to live in Ross Valley, near San Francisco, Cal. The Rand Mines, Ltd., of which Mr. Webber was general manager, was the largest company controlled by Wernher Beit, the leading London house interested in South Africa mining, whose local agents in Johannesburg were H. Eckstein & Co. This firm is now known as the Central Mining & Investment Corpn., and after the departure of Henning Jennings, Mr. Webber was the firm's most valued and confidential advisor and was very highly thought of in mining circles in South Africa. He was a ma of most upright and straightforward high character, plain spoken and sincere; and his recognized high character was one more qualification which aided his great success.

Jan 1, 1923

George Edward WebbeR, a member of the Institute since 1906, died in San Francisco, May 29,1922. Born in Dixmont, Me., in 1852, he went to California in 1857 where he lived until 1883 and received a thorough training in precious metal mining in the employ of his father and J. B. Haggin. In 1883, he went to the Black Hills, South Dakota, as superintendent of the Father DeSmit mine; later the Deadwood Terra also came under his management. These mines are now part of the Homestake Mining Co. In 1889, the Rothchilds asked Hamilton Smith to recommend an engineer to take the place of the late Henning Jennings, who had resigned from the El Calloo Mining Co., of El Calloo, Venezuela, in order that he might proceed to South Africa. Mr. Webber accepted the position, remaining there until 1893 when he returned to the United States on his way to Johannesburg, South Africa, where he had been appointed manager of the Crown Reef Mining Co., Ltd. Early in 1896, he became general manager of the Rand Mines, Ltd., and served in this capacity until 1911. During the latter part of this period, Mr. Webber was active in the greater amalgamations of H. Eckstein & Co., and it was largely on his advice that H. Eckstein & Co. carried out the negotiations preceding the formation of the Crown Mines, Ltd. On his retirement from South Africa, he returned to live in Ross Valley, near San Francisco, Cal. The Rand Mines, Ltd., of which Mr. Webber was general manager, was the largest company controlled by Wernher Beit, the leading London house interested in South Africa mining, whose local agents in Johannesburg were H. Eckstein & Co. This firm is now known as the Central Mining & Investment Corpn., and after the departure of Henning Jennings, Mr. Webber was the firm's most valued and confidential advisor and was very highly thought of in mining circles in South Africa. He was a ma of most upright and straightforward high character, plain spoken and sincere; and his recognized high character was one more qualification which aided his great success.

Jan 1, 1923

By Perry G. Harrison

The increased use of sintering for the beneficiation of iron ores and the reclaiming of flue dust creates a lively interest in sintering costs and economics. The character of material sintered and geographical location of plants so radically alter sintering costs and economics that it is well.to understand at least the basic elements which control such changes. The following cost factors are believed to be roughly approximated for large-scale Dwight-Lloyd continuously operated sinter-machine installations located anywhere. Per Crude Ton Labor, supplies and repairs 0.15 Power 6.5¢ X kw-hr. rate ? Plant overhead and administration 0.05 Depreciation per ton annual capacity 0.05 Fuel: 6 per cent coke breeze or equivalent minimum ? 1 per cent coke breeze additional for each 5 per cent free and combined water in ore or dust ? Ignition distillate at 0.6 gal. per ton ? Per Sinter Ton Royalty on ore 0.10 Royalty on flue dust 0.15 Per Crude Ton "Winter expense"; i. e., the cost of the five months enforced idle . period for plants tied in to Great Lakes transportation season 0.03 Using the foregoing data, it is possible to roughly approximate the cost of efficient sintering at any location for any ore, viz: Per Crude Ton Per Ton Handled Sinter 1. Flue Dust—Steel Plant Locations Sinter recovery, 15 per cent moisture and carbon 85 per cent Labor, supplies and repairs 0.15 0.18 Power 6.5¢ X 1¢ kw-hr. 0.065 0.08 Plant overhead and administration 0.05 0.06 Depreciation per ton 0.05 0.06 Dust handling and preparation 0.10 0.12 Fuel: free, contained in dust Ignition: blast-furnace gas free Royalty 0.15 Total $0.65 Note:—Cost increased by either deficiency or considerable excess of carbon in dust.

Jan 1, 1932

By D. H. Wertz, R. R. Furlong

Dry room equipment at Donora Zinc Works is of the design which prevailed at the time the plant was built in 1915. It consists of 11 adjoining rooms, each being 99 ft long, 11 ft wide, and 7 ft high and having a capacity for 1040 retorts. Heat is supplied by steam coils beneath the slatted wood floor and by warm air ducts at the ceiling. Drying practice is about the same as that generally followed in the industry except that, under normal zinc furnace operations, the maximum drying time is 45 days. During certain seasons of the year the drying process was seriously affected by varying weather conditions which frequently resulted in a scrap loss of 5 to 7 pct. Because of these unfavorable conditions, which caused uneven drying and strains in the retorts, increased retort failures in the zinc furnaces were recorded. Regulation of temperature and humidity under all conditions appeared to be the logical solution of this problem. Controlled drying had been developed for a number of ceramic products and investigation of several such drying processes in this area revealed favorable results. Along with control of drying conditions and the attendant decrease in scrap losses, plant operators also reported a material reduction in drying time. Another factor affecting the decision to proceed with this development was the drastic change in market conditions for retort clay. Curtailment of shipments from the chief source of supply made it necessary to proceed with blending of other available clays, but quality of these clays was questionable for adequate retort life in the 24 hr furnace cycle. Rapid furnace testing of new mixtures was desirable but impossible with the prolonged drying schedule. Therefore development of a controlled drying process for zinc re- torts offered the solution to the problem of rapid testing of retort mixtures. Description of Process and Equipment The freshly extruded retort is cylindrical in shape, 58 in. long, 9 in. id and has 1 1/8 in. side walls. One end is closed and approximately 2 in. thick. The moisture content of this "green" retort is about 17 pct which means a necessary removal of 30 lb of water per retort. Retorts are set on the slatted floor of the dry room with the closed end down. The controlled drying process depends upon the circulation of a large volume of conditioned air at low velocity. To provide for uniform distribu-

Jan 1, 1950

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By Elmer W., Pehrson

NOT much serious consideration was liven to the military aspects of raw materials before World War 1. Following the outbreak of war in Europe in 1914, however. this situation was promptly changed. Disruption of allied shipping and German submarine warfare soon cut off a substantial part of the material the United Staten was accustomed to receiving from overseas. At the same time, raw material requirements rose rapidly as the tempo of industrial preparedness was stepped up in anticipation of war. By April 1917, when we entered the war, serious shortages threatened and consideralde attention was being given to our "deficcient" raw materials. The term "war mineral," began to appear after we became active combatants. But there is no evidence that "strategics" and "critical." as now used, had entered the lexicon of our raw materials experts during the last war nor were there apparently any officially recog¬nized list or definitions of what con¬stituted war materials. According to G. A. Roush in his book, `'Strategic Mineral Supplies," C. K. Leith, while serving as mineral advisor to the War Industries Board. compiled the first unofficial list of deficient minerals in 1917.

Jan 1, 1944

By Arthur Taggart

THE major portion of the work described in this paper was performed by R. W. Young,+ a graduate student in the department of Mining and Metallurgy, Sheffield Scientific School, Yale University, working under a cooperative agreement between the Hardinge Conical Mill Co., the Sheffield Scientific School, and himself. Since this cooperative scheme is at present in effect in the case of a considerable number of other students in the department and since it is the hope of the school that the privilege thus extended may be utilized even more freely in the future by mining and manufacturing companies, it may not be amiss at this point to give a summary of the general plan. Briefly it is as follows: A graduate student, whose undergraduate work in this or other universities shows promise of ability to handle research work, is chosen by conference between the company and instructor involved. The aim of the company in the agreement then entered into is to obtain the solution of one or more of the technical problems with which it may be confronted, or, at the end of 1 or 2 years, to obtain as an employee a man especially trained in its work. As. a means to accomplish one or both of these ends, the company furnishes the machine, apparatus, or material to be tested and pays the student during his graduate work a small salary, usually just sufficient to cover his living expenses, tuition and fees. The aim of the student is special training along a line in which he is particularly interested, the attainment of his advanced degree, and the chance to show to his future employer ability to handle such problems as may be presented to him. In return for the financial aid which he receives he agrees to devote at least half of his working time to the special problem submitted by his company. The other half is devoted to study of the collateral subjects required by the department for the granting of the degree which the student seeks. The student further agrees to enter the employ of the company in question at a wage not greater than that paid in like positions to recent graduates not specially trained and to remain with his employer at such wage for at least 1 year. If the student is to obtain a degree, the special work forming the basis of his investigation must be such as will involve real research and not mere routine manipulation. The subject is chosen by conference between the three parties to the agreement. The work is carried on under the direct supervision of the instructor involved. The school furnishes the general laboratory and library equipment essential to the pursuit of any extended investigation, In

Jan 4, 1917

By B. E. Thompson, H. B. Fuqua

The area discussed herein, commonly known as the North Texas district, embraces the following 10 counties: Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita and Wilbarger. It is underlain by two major structural features. The northernmost portion of the district, including Coolie, Montague, northern Clay, Wichita, Wilbarger, Foard and Hardeman Counties, is underlain by the system of buried mountains known as the Red River uplift, which is parallel to and closely related to the Wichita-Amarillo uplift of Oklahoma and the Texas Panhandle. While the presence of a great majority of the numerous oil fields of the area is traceable to this feature, the production in Archer, southwestern Clay and southeastern Baylor Counties is due to the influence of what is known as the Cisco arch (so called because of its influence on Cisco deposition), the axis of which extends in a northwest-southeast direction across southwestern Wichita County into Archer County. Developments during 1938 Important discoveries in the district were considerably more numerous and of more economic importance than for several years. In addition to a number of small, relatively unimportant discoveries and to the usual local extensions to the various producing fields in the several counties, at least eight fields, most of them apparently of considerable areal extent and importance, were found. The Helmerich and Payne, Incorporated and Blackwell Oil and Gas Company No. 1 Wilson. 4 miles southeast of the town of Holliday, in north central Archer County, encountered a pay of Strawn age at a depth of 3841 to 3858 ft., and was completed for an initial production of 1952 bbl. T'his well opened a new deep pool in the K. M. A. producing zone 8 miles southeast of the K. M. A. production. Subsequently an additional deeper horizon, also of lowcr Strawn age, was discovered by wells that failed to yield commerecial oil from the horizon of the discovery well.

Jan 1, 1939

By H. B. Fuqua, B. E. Thompson

The area discussed herein, commonly known as the North Texas district, embraces the following 10 counties: Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita and Wilbarger. It is underlain by two major structural features. The northernmost portion of the district, including Coolie, Montague, northern Clay, Wichita, Wilbarger, Foard and Hardeman Counties, is underlain by the system of buried mountains known as the Red River uplift, which is parallel to and closely related to the Wichita-Amarillo uplift of Oklahoma and the Texas Panhandle. While the presence of a great majority of the numerous oil fields of the area is traceable to this feature, the production in Archer, southwestern Clay and southeastern Baylor Counties is due to the influence of what is known as the Cisco arch (so called because of its influence on Cisco deposition), the axis of which extends in a northwest-southeast direction across southwestern Wichita County into Archer County. Developments during 1938 Important discoveries in the district were considerably more numerous and of more economic importance than for several years. In addition to a number of small, relatively unimportant discoveries and to the usual local extensions to the various producing fields in the several counties, at least eight fields, most of them apparently of considerable areal extent and importance, were found. The Helmerich and Payne, Incorporated and Blackwell Oil and Gas Company No. 1 Wilson. 4 miles southeast of the town of Holliday, in north central Archer County, encountered a pay of Strawn age at a depth of 3841 to 3858 ft., and was completed for an initial production of 1952 bbl. T'his well opened a new deep pool in the K. M. A. producing zone 8 miles southeast of the K. M. A. production. Subsequently an additional deeper horizon, also of lowcr Strawn age, was discovered by wells that failed to yield commerecial oil from the horizon of the discovery well.

Jan 1, 1939

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The mechanical properties of Ti-C and Ti-C-0 alloys can be altered by heat treatments to dissolve or reject carbon from solid solutions. The maximum strength is obtained by annealing just below the peritectoid temperature. Quenching from the ß-carbide field results in softening. Impact behavior is influenced by the extent of solution of interstitials CARBON is not as important in titanium alloys as it was in earlier years when graphite induction melting was more prevalent. With induction melting, carbon pickup is about 0.5 to 0.8 pct. Cold-mold arc melting with graphite electrodes, which is among the more current methods, results in carbon pickup of 0.1 to 0.2 pct. The titanium-sponge melting stock itself contains about 0.02 to 0.07 pct C, picked up from the magnesium used in the reduction process. Thus, carbon is still one of the more important contaminants in titanium and needs careful study and evaluation in order to understand titanium and titanium alloys. Moreover, it is equally proper to consider carbon as an alloying addition because, in controlled amounts in titanium alloys, it may serve a most useful function. This is particularly the case where the ultimate in toughness is not required. The addition of carbon to titanium results in a peritectoid-type system as illustrated in Fig. 1. The solubility of carbon is seen to be higher in the a phase than in the ß phase in the temperature range of interest. Below the peritectoid temperature, the solubility of carbon in a titanium decreases with decreasing temperature. This type of system permits many microstructural and heat-treatment variations which may influence the properties of the alloys. The study of how the microstructure variations affect mechanical properties is described in this paper. Experimental Procedures The experimental techniques and testing methods used in this work were the same as those described in detail in a previous paper.' No further descriptions will be given except where changes have been made. High purity iodide titanium, produced by the New Jersey Zinc Co., was used in all of the alloys. Carbon additions were made using high purity spectro-graphic carbon electrodes in order to obtain the highest purity carbon available. The alloys were prepared by double arc melting to reduce the possibility of segregation. The alloys were forged at 875°C to ¾ in. round, descaled, vacuum annealed for 5 hr at 900°C to remove the residual hydrogen, and swaged to ¼ in. round at 750°C. All heat treatments were made on material in this initial condition. Two of the early Ti-C ingots were found to have been contaminated in melting. Vacuum-fusion analyses showed that the two contaminated alloys had picked up oxygen, so the test results on these two alloys permitted an evaluation of ternary Ti-C-0 alloys. A list of the alloys and their compositions are given in Table I. Properties of Ti-C Alloys In a peritectoid-type system, such as the Ti-C system, the chief microstructural variable which influences the properties is solid-solution strengthening. For a given composition, it is possible to control the disposition of carbon, either in solid solution or as the compound Tic, by suitable heat treatments. When in solid solution, the carbon present in the alloy makes a definite contribution to the strength of the alloy. However, when present as Tic, it has very little effect on the strength. Other microstructural variables considered in this investigation were transformation structures and grain size. As discussed in subsequent sections, these variables have only a minor effect on properties as compared to the solid-solution effect. Solid-Solution Strengthening: The principal strengthening mechanism for Ti-C alloys has been found to be solid-solution strengthening. Carbon in interstitial solid solution strengthens titanium, but has very little strengthening effect if present as the compound. Since carbon has a higher solubility in

Jan 1, 1956

By M. J. Sinnott

WITH the advent of nodular iron as an engineering material, considerable interest has been shown in developing this material for various applications. Generally the strength, hardness, or ductility are the more common properties used for design purposes but occasionally applications involving a knowledge of the thermal conductivity of the material is required. A search of the literature showed, rather surprisingly, that relatively little work has been done on this property for all types of cast iron. Insufficient data are available on thermal and electrical conductivities to develop the Weidemann-Franz ratio, or the Lorentz relationship, for estimation purposes. There are no data on nodular irons and the published data on malleable irons are quite sketchy. For these reasons the conductivity of the group of nodular irons listed in Table I were measured. Irons I to IV were made in such a fashion as to maintain the carbon and alloy content essentially the same while varying the silicon content. Test specimens were cut from the mid-section of 4-in. keel castings. Iron V is a commercial casting of nodular iron. The test specimen of this iron was cut from the center of a large cast billet 3x10x26 in. All alloys were tested in the as-cast condition. A microstructural examination showed that each iron had spheroidal graphite but the size and distribution varied with the silicon content of the iron. The spheroid size decreased while the number of graphite nodules increased as the silicon content of the iron was increased. The matrix structures of each iron consisted of pearlite and ferrite with the proportions varying from predominantly pearlite in the low-silicon iron to mostly ferrite in the high-silicon iron. The commercial heat, iron V, was predominantly pearlite probably because of its higher manganese and phosphorus content. Two methods for measuring the thermal conductivity were used. The first was a modification of the techniques described by Powell and Hickman and Van Dusen and Shelton,² the second method was a simpler technique described by Jakob and Hawkins." Since the agreement of both methods as tested on two sets of duplicate samples was excellent, the simpler experimental technique was used. The results of the measurements are given in Table II along with a summary of the microstructural constituents. These conductivity data indicate that as the percentage of silicon increases there is a corresponding decrease in the thermal conductivity even though the structure is changing from pearlitic to ferritic. Such a change in microstructure is usually accompanied by an increase in conductivity. A third factor involved in the behavior of these irons is the size and distribution of the graphite nodules. The relative amounts of graphite do not change greatly but the size and distribution do. Generally graphite improves the conductivity but in the present case such an effect is probably masked by the alloying effect from the silicon and its dispersion through the matrix. The thermal conductivity of the nodular irons studied is less than that of regular foundry irons by some 10 to 30 pct and is less than that of regular malleable irons.' The cause of the decreased conductivity is probably the more highly alloyed fer-rites obtained in these irons and the changed mode of distribution of the graphite as compared to the regular foundry irons. References R. W. Powell and M. J. Hickman: Journal Iron and Steel Inst. (1946) 154, No. 2, p. 99. 'M. S. Van Dusen and S. M. Shelton: U. S. Bur. Standards Journal of Research, RP668 (1934) 12, p. 429. ³M. Jakob and G. A. Hawkins: Elements of Heat Transfer and Insulation. 2nd Ed. (1950) New York. John Wiley and Sons. ' J. W. Donaldson: Journal Iron and Steel Inst. (1933) 128, No. 2, p. 255.

Jan 1, 1954

By D. L., Hayes

THE concentration of zinc ore in Wisconsin is a comparatively simple process, although it presents problems that must be overcome in an efficient manner in such a way that installation and operating costs are low. As the ore deposits are small, the first cost of the concentrating plant must be low; while the low margin of profit makes it necessary to have the minimum operating costs. The original mills were copied from those of the Joplin district, as most of them were built and operated by Joplin millmen. These served the purpose well; they made a clean concentrate, which was the chief requirement at that time, as most 'of the mines were' considerably 'richer than the average at the present time, and wages and supplies were also considerably lower. ' The apparatus used at present has changed very little in principle. . The grizzly opening has gradually been increased to 12 in. and sometimes no grizzly 'is used. The crusher, gradually grew in size, the largest crusher has -an opening of about 24 by 13 in. and a 7/8-in. throw on the. eccentric shaft.

Jan 1, 1921

By H. H. Waller, D. L. Monroe, D. P. R. Smyth

ORIGINALLY slusher drift development was conventional, advancing the drift full 10x13-ft size at 6 ft per round. This proved dangerous and costly because the weak fractured rock of the orebody cannot be left raw for any length of time without its reacting with air to cause spalling. With this method of drift development ground conditions were worsened by many blasts and the length of time it was necessary for the drift to remain open. The problem was practically solved by driving 5x7-ft pilot drifts, then enlarging to 10x13-ft raw size by slashing with 50 to 60-ft diamond drill holes. Calculated explosive charges are used to avoid wall and roof shattering. Still more recently jacklegs and sectional steel replaced the diamond drills, resulting in the same work for less than half the cost, see Figs. 1 and 2. Crosscuts at right angles to the main haulage drifts, which cross through the center of the ore-body, divide the ore into 200-ft blocks. Eight slusher drifts on 50-ft centers draw from one block. The slusher floor is 11 ft above the rail, inclined at 1 pct grade, and the top is 18 ft below the undercut. The finished slusher drift is 102.5 or 120 ft long, depending on whether it is north or south of the crosscut. Drawpoints are staggered on each side at 17.5-ft centers. The completed drift is concreted and has an inclined ramp and a vent at the back. When crosscuts and gangways have been excavated and concreted and slusher stations installed, slusher drift development is carried out in 10 clear-cut stages: 1—Pilot drift is driven full length, 5x7 ft. 2—Station is excavated at half-way point in pilot drift. 3—Pilot drift is enlarged to slusher drift size by drilling. 4—Lower part of slash is blasted and mucked for floor concrete. 5—Floor is poured. 6—Inside upper half of slusher drift is blasted, mucked, and concreted. 7—Outside upper half of slusher drift is blasted, mucked, and concreted. 8—Drawpoints are excavated. 9—Drawpoints are concreted. 10—Concrete ramp and sheave protection recess are constructed at back end of slusher drift. A 5x7-ft pilot drift is driven full length on the center line of the proposed slusher drift using a jackleg and detachable bits on 7/8-in. hexagon steel. A 10-hp air-driven slusher and 36-in. scraper pull muck directly into cars in the main haulage crosscut, see Fig. 2. Operations are on a three-shift basis. One man mucks the previous round, drills, and blasts his round in a shift. Average advance is 5 ft per shift. When the pilot drift is completed, 7 ft of drift in the center section is enlarged to full raw slusher drift size of 10x13 ft, for the set-up to drill long slash holes. The pilot drift is slashed to full raw size from this station with jacklegs and tungsten carbide chisel bits on 7/8-in. sectional steel. Crews line the holes without trouble, working from controls established by the engineers, and the pattern of holes for the slash is arranged to give the least shattering effect

Jan 1, 1955

By John Tyssowski

IN 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temper-atures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several parti-cles had become one unit. From this dis-covery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the appli-cation of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper pro-duced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable

Jan 1, 1940

The pressure of the gas in equilibrium with sphalerite has been determined in the temperature range of 680' to 825°C, using the Knudsen orifice method. A comparison of these experimental pressures with those calculated from thermal data and from other equilibrium measurements shows that the vapor above sphalerite is predominantly dissociated ZnS. Equations have been given for correctly calculating dissociation pressures using the Knudsen orifice method. It has been shown that the experimentally determined pressure is the same, whether the zinc sulphide is sphalerite or not, or a mixture of wurtzite and sphalerite. CONFLICTING points of view appear in the literature on the constitution of the vapor in equilibrium with solid zinc sulphide in the vicinity of 800°C. By comparing the dissociation pressure calculated from thermodynamic data and the vapor-pressure determination of ZnS by Veselovski,1 Lumsden2 has concluded that the vapor consists largely of dissociated ZnS. Sen Gupta,' however, concludes from his spectroscopic determinations that the vapor is largely ZnS molecules. In view of the fact that the thermodynamically calculated' dissociation pressure is higher than that experimentally measured by Veselovski, it seemed in order to repeat Veselovski's measurements. Experimental Procedure The method used for the determination of the pressures in this papel- is the Knudsen effusion cell. The apparatus and procedure were described in a previous paper- from this laboratory on the determination of the vapor pressure of silver. The only difference is that the Knudsen cell in this work is made from platinum and there is no external cover around the cell. The cell is an ordinary platinum crucible of 2.2 cm top diameter with a capsule cover. It was thought that platinum might stand up at these temperatures to the solid and gaseous ZnS, since it was found that the weight of the platinum cell itself did not change appreciably on heating ZnS in it at the working temperatures. To insure that reaction of the zinc sulphide with the cell was not giving' a false value, a stabilized zirconia cell was employed for check runs. Fig. 1 shows the comparison, which is satisfactory. Veselovski previously had measured the vapor pressure of ZnS using a silica Knudsen effusion cell. On repeating his experiment in this laboratory, it was found that ZnS at-tacked the silica cell, giving it a marked frosty appearance. This led to the belief that Veselovski's result:; may be in error. Also, he was operating at pressures above the range ordinarily considered safe for the Knudsen method. The effusion rate was measured by weighing the cell before and after each run. The weight loss during heating to temperature and cooling down was measured and subtracted from the weight loss during the actual run. The zinc sulphide used in this investigation was from two sources: Fisher cp grade, and a sample of pure sphalerite supplied by Mr. E. A. Anderson of the New Jersey Zinc Co. Before and after the series of runs with Fisher ZnS, X-ray analysis showed that both wurtzite and sphalerite were present. However, the ratio of sphalerite to wurtzite increased. All measurements were made below the transition temperature which has been reported" to be 1020°C. The data obtained in this investigation are tabulated in Table I. The pressure was calculated by the usual Knudsen formula" on the assumption that ZnS molecules were effusing. From these data, using pure sphalerite in the platinum Knudsen cell, the vapor pressure of ZnS, in mm of Hg, as a function of temperature is given by the solid line in Fig. 1. The best straight line, as determined by the method of least squares, is given by 14405 logpzns =-14405/T +11.032. A comparison of these results with Veselovski's shows that his results are about 50 pct lower. Discussion The vapor in equilibrium with solid zinc sulphide in the temperature range of this study will consist of Zn, S2, and ZnS mol, since other species of zinc and sulphur' are relatively unstable. The question to be settled is whether or not ZnS is largely dissociated. The derivation8 which follows gives the method of calculating the pressure of zinc and sulphur over solid ZnS, assuming complete dissociation, from Knudsen cell data. The free energy of the reaction 2 ZnS(solid) ? 2 Zn(gas) + S2(gas) is given by ?F?° = -RT In K = —RT In p12p2 where p1 is the zinc pressure and p is the sulphur pressure. If dissociation occurs in a closed system,

Jan 1, 1955