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By John E. Conley

THE production of lime by the burning or calcination of limestone, including all varieties from true dolomites and magnesian limestones to high-calcium types, continues as one of the essential basic industries. In 1937, a total of 4,124,165 tons of lime valued at approximately $30,091,000 was produced in the United States.1 The importance of any contribution to our knowledge on the mechanism of the lime-burning process is, therefore, obvious. The burning of limestone has been practiced since the earliest days of our civilization, and the literature on the various phases of the industry is voluminous. Calcination of the various types of limestone has been studied by many previous investigators, but some points require additional research. Each occurrence of limestone provides an opportunity for specific investigation, because the characteristics of stones in different localities vary Knibbs13 has given an excellent discussion of available data on the theory of lime and magnesia burning. The thermal dissociation of calcium carbonate has been studied more recently by Johnston,2 Smyth and Adams,3 Ralston et al.,4 Furnas,5 Potapenko,6 and Southard and Royster.7 As a result of these investigations the dissociation temperature at atmospheric pressure has been established as 894º to 898º C. The dissociation of dolomite and magnesite, although studied by several investigator,4, 6, 8 still requires clarification by additional data. The calcination of limestone was studied for a twofold purpose: (1) to extend our information on the mechanism of the lime-burning process and (2) to standardize the conditions for calcination of high-calcium and dolomitic limestones for subsequent hydration tests on the lime.

Jan 1, 1939

By S. E. Maddigan, B. R. Zimmerman

MOST metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un- soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample appeared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.1 The true potentialities of the technique are revealed by comparison of Figs. 2a and 2b, which are respectively a- photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated lumps of lead. Fig. ab, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,1,2,3 but for clarity a brief resumé will be given here. As is well known, when a beam of X-rays is transmitted through a layer of homogeneous material, the intensity is reduced according to the relation:[ ]

Jan 1, 1944

By M. Khorouzan, L. Thomas

Designers of semiconductor devices have been strivi,ng to resolve problems associated with Au-A1 alloys in bonded in.tercomzeclions. One approach now being- used is that of waintaining a physical seyav-atioz between the two metals in bond areas. This is accolrzplished by alunzincnz-plating a bonding area on the tips oJ the kovar leads and using alcminurn wires to join the senzicondictor device to the leads. The portion of the kovar lead which is on the externul side of the sealed package is gold-plated to provide an oxide-free surface for soldering or welding. A discoloration condition originally thought to be sinilar to purple plague, occuving in the yluled uluninur bonding area after package sealing, has been investigated to determine its efiects ipm bond integrity. Electron-micro-probe analysis determined that no1 only gold, but lead, zinc, and silicon were also present in the discolored area. A series of samples conlaining' conkrolled umonts of these inzpitrities weve prepared and subjected to a sil.zuluted sealing process. The investigations swcued that, of the contawiinants, only zinc toas detrinenlul to Lhe bond integily. The discoloration condition itself was found not to be detrimental to the bond integrity. DESIGNERS of semiconductor devices have been striving to resolve problems associated with Au-A1 alloys in bonded interconnections. One approach now being used is that of maintaining a physical separation between the two metals in bond areas. This is accomplished by aluminum plating a bonding area on the tips of the kovar leads and using aluminum wires to join the semiconductor device to the kovar leads. The portion of the kovar lead which is on the external side of the sealed package is gold-plated to provide an oxide-free surface for soldering or welding. Contamination as evidenced by discoloration of the aluminum-plated area was observed in a number of integrated circuits undergoing examination for defect characteristics which cause electrical failures.' This paper contains the results of an investigation to determine the nature of this discoloration, its cause, and its effect upon the integrity of the interconnection bond. I) THE NATURE AND EXTENT OF ALUMINUM-BOND CONTAMINATION The initial hypothesis in the investigation was that the discoloration was caused by reaction of the aluminum film with some unknown contaminants during the sealing of the hermetically sealed integrated-circuit flat package. The package is a rectangular ceramic container sealed with glass which surrounds the kovar leads as well as joining the top to the bottom. The seal is made hermetic by heating and cooling the package to devitrify the glass. In the case of the packages under investigation, the hermetic sealing had been accomplished with dry air as internal atmosphere. The apparent effect of contaminations as observed by microscopic examination was the formation of surface oxides having variations in color encompassing the whole spectrum of visible light. The contamination appeared to be related to one of the more notorious examples of these colorations, the so called purple plague.' In addition to purple plague, Fig. 1 shows the tarnish in the luster of the aluminized surface in the bond area which had been observed in many of the integrated circuits. To identify the contaminant in the bond area electron-probe microanalysis techniques were used.3 Fig. 2 shows the result of this analysis. The contaminants identified were gold, aluminum, zinc, lead, silicon, and cobalt. Fig. 2(a) is a back-scatter display of the area under study. The back-scattered electrons provide a general indication of the distribution of elements in the specimen surface. Elements with higher atomic number scatter more electrons back from the surface and are seen as light areas in the picture. The sample current, Fig. 2(b), is the amount of current conducted by the specimen as a result of electron-beam striking it and is an indication of element distribution. The Sample current is the reverse of back-scatter and complements it. Other pictures in Fig. 2 are produced by characteristic X-rays generated by the elements, allowing the isolation of the element of interest. The isolated element appears white and all other elements are dark. In this manner a comparative study provides a correlation between different surface areas and the elements which are in these areas. The area covered by the gold film, Fig. 2(c), shows that the boundary between the gold film and the kovar is not sharp as expected and that some sort of diffusion has taken place. Fig. 2(c) shows that some gold particles have been carried to the bond area and are in the proximity of the bonded wire in spite of the presence of a physical barrier in the form of the un-

Jan 1, 1967

By James A. Soles

Concrete is a complex, multicomponent mass whose stability is dependent on three principal variables: quality of the mix, its composition, and environment of the site. The aggregate is only one component, but its constituent minerals may react in unfavorable regimes and, given sufficient time, destroy the concrete. Therefore, besides ensuring that a concrete will meet the strength requirements of a structure, the concrete engineer must be confident that the mortar and aggregates will resist destructive processes. This paper reviews the principal causes and effects of aggregate instability, notes reactions of certain phases, and suggests precautionary measures that can be taken to extend the useful life of concrete structures.

Jan 1, 1984

By T. N. Williamson

The art of drilling tunnels is still in its infancy, although it is 70 years since the first tunnel driver was put into operation. (It was used to drive 6000 ft of tunnel under the English Channel.) But during the next 60 years neither government agencies nor private enterprise could find much of a future in tunnel drivers. It was difficult to justify the heavy investments, labor was opposed to the machines, and there had been some spectacular failures. In the last ten years, however, there have been changes. Tunnel drivers are being tried with increasing frequency-in spite of the fact that a large number of them have had to be abandoned on site.

Jan 7, 1965

By D. R. Mitchell

This paper discusses some of the fundamental physical and chemical characteristics of coal in Illinois that affect its preparation for the market. At the present time preparation consists almost entirely of sizing and hand-picking. The washing of coal has almost entirely disappeared from the state. This is a rather startling fact when one considers that in the year 1908 Illinois outranked all other states in the quantity of coal washed and a few years later, in 1912, 85 washing plants were reported. Two reasons are apparent for this change. One, which is probably the most important, is that immense areas of comparatively clean coal were opened; the other is that many of the early washing plants were inefficient, so that washed coal was looked upon with disfavor in many trade centers. Objectives of Operators Some of the outstanding preparation aims being given due consideration by operating men are: 1. The greatest possible production of lump and domestic sizes which bring in the market at least $1 per ton more than the fine sizes or screenings. 2. Efficient screen sizing with as little breakage as is consistent with economical operation. 3. The removal of extraneous ash and sulfur. 4. Utilization of low-priced screenings. 5. Suppression of dust in domestic coal shipments. Preparation Underground To get the greatest possible production of the larger sizes, preparation must start at the face. Improvements in blasting and loading have increased the sizes larger than 2 in. by as much as 20 per cent. at some mines. Tiffany and McKitterickl report the results of an investigation they made at a mine in southern Illinois in which, by a carefully controlled

Jan 1, 1931

Steel Tape The new Lufkin Royal Ni-Clad steel tape, made in 25, 50, 75, and 100-ft sizes, is stated to cost less than any other steel tape on the market. Figures and graduations are an integral part of the steel and the nickel plated surface is rust and corrosion resistant. Circle No. 1 Lift A manually operated and propelled hydraulic lift marketed by Century Products Co. weighs only [ ] 150 lb, but the 23x24 in. platform will raise 1000 lb from floor level to 4 ft height. Circle No. 2 Scintillation Counter The Scintillator from Precision Radiation Instruments, stated to have 100 times the sensitivity of the Geiger counter, is suitable for prospecting and may be operated from plane or moving vehicle. The instrument is contained in a 2-lb probe and the belt mounted battery box weighs less than 4 lb. Circle No. 3 Generators Wincharger Corp. announces development of a Speedy-Shift wheel-barrow base type attachment for model 700, 1800 and 5000 engine-generator sets. Portability of the engine-generator sets themselves has been improved by belted construction for higher operating speed and maximum weight reduction. Circle No. 4

Jan 1, 1952

By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.'- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin' has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled' that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By Arthur F. Taggart

PROGRESS in a technical art is of several kinds. It springs .from many diverse sources. It comprises invention, mechanical improvement, operating advance, analytical study, education. Invention is, by definition, a relatively great, essentially individual step, taken quickly. Operating advance is the slow, cumulated march of practice; in contrast, it moves at the pace of the tortoise, but over, the years its effects rival and, in some cases, surpass those of invention. Mechanical improvement- is a usual concomitant of the reduction of invention. to operating practice; thereafter it is a primary tool of operating advance. Analytical study is the process of mental digestion of the fruits of invention and practice. Its purpose is to render these into a form assimilable by the art as a whole, and by the perennial crop of would be practitioners. Education, disseminating the results of such study, consolidates and maintains the positions gained. Thus, slowly at first, but continuously accelerating, the tide of progress grows- to flood. Such growth, in mathematical parlance, is expressible in the general form y = mxn, where x is time, n is some positive number greater than one, m is another positive number, and y is the state of the action at instant x. When n is 2, the readers will recognize the graph of the equation as one branch of the familiar square parabola, whose property it is to become parallel to the y-axis; i.e., to move at an infinite rate, in that never-never

Jan 1, 1947

MONTANA SECTION J. L. BRUCE, Chairman W. C. SIDERFIN, Vice-Chairman WALTER E. GABY, Secretary-Treasurer, 834 W. Granite St., Butte, Mont. N. B. BRALY W. T. BURNS A special meeting of the Directors of the Montana Section was held on July 24, 1916, with W. C. Siderfin, Vice-Chairman, presiding. The meeting was called for the purpose of electing a Secretary-Treasurer to fill the, vacancy created by the resignation of M. H. Gidel. Upon proper motions, the resignation of M. H. Gidel was, accepted, and Walter E. Gaby was elected to fill the office for the balance of the fiscal year. No further business was transacted, and upon motion the meeting adjourned WALTER E. GABY, Secretary.

Jan 9, 1916

ALKALINE LEACHING; SODIUM HYDROXIDE U.S. 4,091,071 -In the alkaline digestion of bauxite containing goethite, boehmite and/or diaspore, the process is accelerated by adding to the digestion mass an optimum proportion of calcium oxide and divalent manganese ions, advantageously in the form of a calcium carbonate-containing manganese oxide ore, whereby goethite is transformed into hematite, the alumina yield increased, and loss of caustic soda values minimized. J. Boros, assigned to Femipari Kutato Intezet, Aluterv Alumiumipari Tervezo Vallalat and Almasfuzitoi Timfoldgyar. May 23, 1978. 7 pp. Filed: 12-23-75 (643,670). Priority: Hungary, 12-24-74 (AU 330). Same: British 1,528,146, dated Oct. 11, 1978.

Jan 1, 1979

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By A. M. Radigan, W. G. Prast

Various industrial minerals that are traded internationally receive support from governments, enabling these materials to be more competitive. The role of government in encouraging nonmetallics exports ranges from the ownership of an integrated mining company to partial or selective government ownership, to the sponsorship of exporter organizations. In certain cases, regional governments have a direct stake in the industrial minerals industry. This paper assesses the commercial impact of these involvements.

Jan 1, 1984

By O. C. Ralston

THE use of copper sulfate for improving the flotation behavior of sphalerite is probably at least 15 years old. The original discovery of its activating influence is somewhat obscure. The story goes that in the mill at Mascot, Tenn., its favorable action was discovered by accident, early in 1914, as follows: The original laboratory test work on a sphalerite ore gave favorable flotation results, but after a mill had been built the flotation concentration of the ore was very unsatisfactory. In diagnosing the probable reasons, one fact pointed out was that the laboratory test machine had been constructed of bronze whereas the commercial machine allowed pulp to come in contact only with wood and iron. A plate of sheet copper was hung in the flotation machine and results immediately improved. At first fanciful explanations of electrolytic and electrostatic behavior were given credence, but when the copper plate was removed and a small amount of copper sulfate substituted in the pulp an even more favorable result was obtained. Toward the end of 1914 copper sulfate was also adopted in the acid flotation circuit of the Butte and Superior Copper Co. Just who is responsible for the original discovery the present writers do not know: It seems strange that in that era of flotation litigation this discovery was not patented. While for pragmatic purposes it may be sufficient to know that the mere addition of copper compounds to a flotation pulp is sufficient to activate the flotation of the sphalerite, for scientific purposes it is quite desirable to know more about how the action takes place. It is the purpose of this paper to present certain evidence dealing with the mechanism of the beneficial effect. The description of the effect as activation in contradistinction to depression is now common in both the English and German languages. It makes no assumptions as to whether the zinc sulfide surfaces have been filmed with copper compounds. In fact, the principal differences of opinion expressed in the literature deal with whether there is an actual formation of CuS (or even Cu2S) on the surface of the sphalerite.

Jan 1, 1929

Located 19 km (12 miles) north of the Carlin gold mine and 43 km (27 miles) north of Carlin, Nevada, is Carlin Gold Mining Company's Bootstrap mine. This deposit is similar in character to the Carlin ore, except it occurs in the upper plate formation of the Roberts thrust fault rather than in the lower plate rocks. The deposit was discovered over 50 years ago and operated on a small scale in the early 1960s using vat cyanide leaching. Newmont Mining Corporation acquired the property in 1967, and from an open pit mined 650,000 mt (717,000 st) of ore which was trucked to the Carlin conventional cyanide plant. (See Gold and Silver Cyanidation Plant Practice by F. W. McQuiston, Jr. and R. S. Shoemaker, Society of Mining Engineers, AIME, 1975. ) With the same grade of ore, the gold recovery by conventional methods is somewhat lower than that of the Carlin ore, even with a finer grind. Leaching tests were first conducted by the United States Bureau of Mines in 1968; and in 1971, ‘72, Carlin conducted extensive cyanidation investigations by bottle testing, simulated heap leaching in tall columns, and small scale pad heap leaches. Gold extractions ranged from 55% to 95% with low reagent consumptions. In 1974, a 545 mt (600 st) heap leach test was made at Carlin on pit-run low-grade material assaying 1.37 g per mt (0.04 oz per st). In a six week period the extraction of gold was 47.57'0. Carlin uses atomic absorption analyses on cyanide leach liquors to determine potential leach ore grade rather than fire assaying because it gives a more practical assessment of leach recovery than does fire assaying, which accounts for the total gold content. Before open-pit mining was started, plans were made to heap leach, the ore at Bootstrap which was too low grade for transport to Carlin. The topsoil outside of the designed pit area overlaid ancient lakebed clays which were found suitable for compaction to form an impervious base on which the dumps to be leached could be placed. By using the cost of truck haulage and milling at the Carlin plant and the price of gold 'at that time, a cutoff grade was established which resulted in the gold content of the first 150,000 mt (165,000 st) of the heap leaching ore being 1.51 g per mt (0.044 oz per st). An additional 500,000 mt (552,000 st) of lower grade material, assaying 0.96 g per mt (0.028 oz per st), is available for leaching as economics permit.

Jan 1, 1981

By Colin G. ink

OUTSTANDI'NG in progress among the less familiar 'metals during 1936 is the electrolytic production of 99.9 per cent manganese meta1 readily and many quantity. Strictly speaking, manganese should not' be classed as 'a rare metal, since there is 800 times as much manganese in the earth's crust as there is zinc or lead. But manganese' as a metal is rare, just as titanium metal is rare though titanium is five times as abundant in the earth's crust as manganese.

Jan 1, 1937

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By P. R. Martin, R. B. Kelly

Drilling in Central Texas during 1933 was confined, for the most part, to the search for new serpentine plugs. Bastrop County led in this particular activity, with 50 completions during the 12 months' period, 12 of which were productive. Only one new field was opened in Central Texas during the year, it being known as "Hilbig" (Bastrop County) and was discovered by the Humble Oil & Refining Co. The finding of commercial production in the serpentine at 2500 ft. led to further search in this and surrounding counties, but without success. Bexar County actually provided the greatest amount of drilling but the activity was limited to shallow development from 400 to 2000 ft. The Edwards limestone pay, which has been such a factor in past years, received but slight attention during 1933. Unsuccessful exploration was carried on in Lee and Burleson counties. With the exception of Freestone County, the Woodbine sand area was given even less consideration. This county, because of its close proximity to Anderson and Leon counties, saw a very active leasing campaign and several important tests drilled. In Central Texas, 252 wells were completed in 1933, and of this number 52, or 21 per cent, were productive. Hilbig Field The discovery well, Humble Oil & Refining Company's Annie Hassler No. 1, was completed Feb. 16, 1933, for an initial production of 65 bbl. the first hour, through tubing and 1/2-in. choke. The production was found in serpentine at 2468 ft. and tested 37.2" A.P.I. gravity. Twelve producing wells were drilled during the year and served to indicate that not more than 300 acres would comprise the entire field. Daily production at the end of the year was 775 bbl., although the field potential was 18,240 bbl. daily through 1-in. choke. The field adapts itself to pressure maintenance, and this scientific handling is being undertaken by the Humble Oil & Refining Co. through one injection well. It is the only area in the district where work of this nature is under way. Proration of Oil The more stringent application of proration in 1933 did not affect materially the producing fields in Central Texas. This is accounted for

Jan 1, 1934

By Charles Catlett

(Chattanooga Meeting, October, 1M.) THE terms " developed " and " undeveloped " are necessarily relative and cover a wide range; but the latter is here applied to cases in which the information at hand falls short of a clear demonstration of values, and conclusions must be reached from a study of the geological conditions of the particular deposit, interpreted in the light of similar and closely related deposits. Such an inquiry might be characterized as an effort to reach reliable conclusions from insufficient data. But the engineer engaged in commercial work finds himself often face to face with apparently such problems; and while he may realize with regret that a small amount of intelligent development would add enormously to the value of his conclusions, he is compelled to recognize the demand of a business situation for a prompt decision as the basis of immediate action. In a case within my knowledge, the question involved was the purchase of 50,000 acres of coal-land, and 10 days was the limit within which this question must be decided. Of course, it was impossible to make a satisfactory examination within that time; but the 'instructions were "to make the most complete examination and the most positive recommendation possible." Such instructions are often given; for, no matter how much time an investor may have, he is likely to put of his decision until the last moment, and then discover that he needs more light and advice. It does not follow that engineers, after full explanation and mutual understanding of the situation, should decline to undertake examinations thus limited. In the case just mentioned, while only the broadest view was possible, half the time available was sufficient to show that the property was a good purchase. The timber alone was subsequently resold for more than the entire purchase-price of the

Mar 1, 1909