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By E. Seidl

THE basic material for testing aluminum, copper and zinc is a cast metal, principally in the form of wire bars (Figs. 1 to 3) and plates for the produc- tion of sheets or strips, (Figs. 4 to 7). Experience has proved that the chemical and crystallographic proper-ties of such cast metal exercise a certain influence when it is being worked, which is usually done while the metal is hot. In a chemical sense the slight impurities, which even the purest industrial metal contains, have a disturbing effect. They settle either along the outside limits of granulation, as in the case of aluminum and copper, or else in the interior of the crystal, as in the case of zinc; but frequently are also found accumulating at certain points (formation of the blowholes and skin) (Fig. 7). The crystallographic character of the metals is either that of uniformly fine granulation, or else there occurs a certain distinct casting texture marked by sharply defined cooling conditions and consisting of crys-tals of a pronounced stalk-like or blade form. Since we generally distinguish between a crystal texture and a crystal structure, the term crystal texture is used here for the arrangement of the crystals relative to each other and their microscopic composition; crystallic structure is used to mean the radioscopically ascertain-able structure of the crystal. The influence of the impurities and of the crystalline character on the working of the metals has been fre-quently pointed out in practice as well as in science.

Jan 11, 1927

By V. Pasupathi, R. E. Hummel, J. W. Koger

Specimens of P1 brass were plastically deformed at room temperature to various degrees of deformation and subsequently cooled in order to transform them to low-temperature martensite. Deformation shifts Ms. A, , and the temperature of minimum resistivity to lower temperatures, and also decreases the temperature coefficient of electrical resistivity. These properties change rapidly up to about 15 pct reduction but vary very little with higher deformation. The possible relationships between martensite formed by deformation and the M, temperature of low-temperature martensite are discussed. Evidence is given that deformation martensite delays the formation of low-temperature martensite. BETA' brass undergoes at least two different types of martensitic transformations. One of these transformations (B1- B2) was first observed by Kaminski and ~urdjumov' and occurs when 81 brass with a zinc content between 38 and 42 wt pct (quenched from the single-phase region) is cooled below room temperature. Jollev and Hull' determined the structure of 0" from X-ray and electron-diffraction data as ortho-rhombic. Kunze came to the conclusion that the super-lattice cell of 0" is one-sided face-centered triclinic (pseudomonoclinic). The second martensitic transformation (B1-A1) occurs when the specimens are deformed at or somewhat above room temperature. This type of martensite will be called deformation martensite. Horn-bogen, Segmuller, and Wassermann4 determined the structure of deformation martensite to be bct. (An intermediate phase, az, occurs before the final phase appears.) At deformations higher than 70 pct, a, transforms into a.4 A critical temperature Md exists above which no transformation occurs during deformation and is estimated to be around 400°C in P1 brass.5 This martensite has elastic properties.6 When the sample is stressed, martensitic plates appear; when the stress is released, the plates disappear. The present paper studies the effect of deformation martensite on the formation of low-temperature martensite. The experiments involved samples of 8, brass which were plastically deformed by various amounts and were subsequently cooled below the transformation temperature. EXPERIMENTAL PROCEDURE The 13 brass investigated was made from 99.999 pct pure copper and 99.9999 pct pure zinc and contained 38.8 wt pct Zn. The specimens, consisting of foils 0.1 mm in thickness, were heat-treated at 8'70°C for 15 min in an argon atmosphere and then quenched into ice water. They were then deformed by cold rolling and subsequently cooled at a rate of 1°C per min. The martensitic transformation that occurred during cooling was followed by electrical resistivity measurements. The resistance measurement technique and its accuracy have been described in a previous paper. Because the transformation 81 —-8" occurs below room temperature, the samples were placed in a cryo-stat which contained isopentane as a cooling medium. The isopentane was cooled by liquid nitrogen pumped under pressure through a 15-ft coil of copper tubing which was immersed in the isopentane. The nitrogen flow was regulated by a temperature controller using two thermistors in the cooling medium. The cryogenic liquid could be heated with an immersion heater. The useful temperature range with this device was from +25° to approximately -155~C. EXPERIMENTAL RESULTS Resistivity Measurements. The following abbreviations are used in this paper to label the characteristic temperatures during the martensitic transformation. M, is the starting point of the martensitic transformation and is defined as that temperature where the resistivity vs temperature curve on cooling first deviates from a straight line. Mf is the temperature at which the martensitic transformation is completed. On reheating, the transformation from martensite to the parent phase starts at a temperature A, and ceases at a temperature Af. Fig. 1 presents five different resistivity vs temperature curves corresponding to the transformation of brass from Dl to 8" after different degrees of reduction in thickness. The following observations can be made from these curves. 1) With increasing degree of deformation the Ms temperature is shifted to lower temperatures. This shift ranges up to 35°C compared to the undeformed state. This is also indicated in Fig. 2, where AM, (the shift of Ms, compared to the undeformed state) is plotted vs the degree of deformation. AM, increases rapidly until a reduction of about 15 pct is reached. With higher deformations, no additional increase in AM, was found. 2) With increasing degree of deformation the temperature of minimum resistivity (M) is also shifted to lower temperatures. The shift, attains a maximum of about 61°C compared to the undeformed state. In Fig. 3, AM is plotted as a function of deformation. It can be seen that, as in 1 above, AM increases rapidly and no further shift of M occurs for deformations greater than 15 pct. 3) The temperature coefficient of resistivity, is given by the slopes (dp/dT) of the linear portions of

Jan 1, 1969

By Frank Haas

Many articles on the physical properties of fire damp have appeared in the Transactions and elsewhere but practically nothing has been written in regard to its occurrence or fluctuation in quantity in an ordinary mine. After the Monongah explosion in 1907, with the loss of 361 lives, the Consolidation Coal Co. sought a method by which such catastrophes could be prevented. While the cause of this particular explosion was attributed to coal dust, some of those acquainted with the mine thought that fire damp was involved, if it was not the initial cause. So the literature on the subject was studied and mines where similar conditions prevailed in this country and Europe, were visited, with the view of establishing some system by which gas could be more easily detected and controlled. The results of this study were disappointing for no method was found other than the time-honored fire boss with his safety lamp, with some variations in the rules and regulations governing his inspections and reports. Duties of the Fire Boss Pending the development of a better method, it was decided to standardize and perfect the duties of the fire boss and the reports based on his observations. Those who were then in service were closely examined, various lamps were experimented with and the lamps and individuals tested under known conditions. It was found that a fire boss could tell whether gas was present but his estimate of quantity was not even an approximation; therefore, while the services of fire bosses were indispen-sible there was need of additional information by which the quantity of gas could be estimated with some precision in order to determine its variation from time to time. Chemical Process for Determination of Methane After considering all methods known at that time a chemical process was adopted. The principles involved in the process are that in an enclosed receptacle, in the presence of excess air, methane will be completely burned by means of a hot platinum wire to carbon dioxide and

Jan 1, 1927

By R. I. Jaffee, J. G. Dunleavy, H. R. Ogden, Webster Hodge

INTRODUCTION EARLY in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fick1 and Ruer and Goerens2 definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line off immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 1570°C in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Ford5 have shown that, when hot-rolled copper iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have 150,000 psi tensile strength, and about 41 pct IACS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult, In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation 0f this type of alloy. As a result 0f this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1948

By G. F. Jr. Butterworth

THE metallographic structures most frequently encountered in rifle barrels, and which are illustrated by the accompanying photomicrographs, fall naturally into two groups, distinguished by the method used to produce in the stock a physical condition having the requisite properties. The first group consists 'of "rolled" barrels; that is, barrels subjected to hot working by rolling in or near the critical range. In the second group, the stock, which is smaller in diameter than the first, is upset to form the butt end and is then heat-treated by giving it a quench and a draw. These barrels will be referred to as "heat-treated" barrels. The structure of the rolled barrels resembles closely that of the same steel after annealing. There is the same network of excess ferrite outlining the grain boundaries, but the grains themselves are composed of sorbite rather than pearlite. The grain size is closely related to the rolling temperature. The critical-point curves of this grade of steel, which is approximately 0.50 to 0.60 per cent. of carbon and 1.00 to 1.30 per cent. of manganese, show a single very pronounced point between 1300° and 1350° F. (704° and 732° C.). Barrels rolled within this temperature range give an exceedingly fine grain, shown in Fig. 1. In fact, the grains may be so fine that, at a low magnification, they may be confused with the heat-treated structure discussed below, Fig. 6. A magnification of 500 diameters, however, will always resolve a rolled barrel into the characteristic structure, shown in Fig. 2. As the temperature is increased, the grains are found to be larger. If, on the other hand, the rolling temperature is below the critical range, the structure previous to rolling will not be obliterated, the only effect of rolling being to elongate the coarse sorbite grains in the direction of rolling, Fig. 3. This distortion is greatest at the muzzle. Heat-treated barrels are quenched in oil from above the critical range, which should give a martensitic structure, Fig. 4, but the presence of some troostite in the martensite is frequently noted when the quench has not been sufficiently drastic, Fig. 5. The structure brought about by the subsequent draw is not so striking, though quite as typical. It is sorbitic or sorbito-pearlitic, and under- a low magnification appears

Jan 7, 1919

By Barnabas Bryan

During the boom period of 1928 and 1929, several oil companies took advantage of high security prices to sell stocks, thereby securing money for the company very cheaply. Few if any of those companies realized that the money received was not at all cheap in view of the fact that it was for investment in fixed assets at inflated prices. Suppose a company borrowed twenty millions of dollars to expand its marketing facilities during the boom. It diluted its capital and acquired fixed property which could not earn its interest requirements during the following deflation and therefore consumed income from other company activities. The company also had to stand the deflation in the capital value of all the property it bought. Since the mistaken expansion during the boom accelerated the decline in net income during deflation, the financial position of the company was harmed in proportion to the amount of that expansion. Thus the company was unable to get money to buy fixed assets in the depression when all property is cheap. The same condition holds for the company that sold common stock for the purpose of developing potential production in a newly discovered oil field. Regardless of what the ultimate value of the new field may be, potential production does not increase the net income of the company. The difficulty of meeting the enlarged dividend requirements due to the increased number of shares outstanding impairs the financial position of the company during deflation in some relation to the probability of decreased dividends. This company also is not in a position to expand during the depression when properties and companies can be bought for a fraction of their real value. Expansion of fixed assets during boom times has been the ruin of many otherwise good companies. Some of those which most extensively bought property during the post-war boom have not yet recovered. A number of cases could be cited in sugar, leather, fertilizer and wool. This does not seem to be governed by the quality of the property bought, for examination shows the assets to have been of individual high quality in many cases. When recovery is long deferred it is likely to be true, as in sugar or textiles, that the industry has a large "potential" capacity for overproduction.

Jan 1, 1931

By E. C. Harder

CERTAIN typical characteristics of bauxites, ores of aluminum permit their classification into a number of categories, each of which has special features that enable grouping within it deposits from widely scattered bauxite fields. There may be local variations in conditions that have introduced differences of lesser importance between similar deposits in different fields, resulting perhaps from the influence of factors other than those that have produced the distinguishing features of each of the different groups, but in general the similarity between the deposits in each group is sufficiently striking to make the grouping indicated of interest. Several factors and conditions enter into the decomposition process that results in the development of bauxites and laterites and affects their character. The principal conditions favoring optimum bauxitization are: (1) pres- ence of rocks with easily soluble minerals yielding residues rich in alumina; (2) effective rock porosity, enabling easy access and free circulation of water; (3) normal to abundant rainfall alternating with dry periods; (4) vegetation, including bacteria, advantageously distributed; (5) available sources of appropriate solution and precipitation agencies; (6) a tropical or at least a warm climate; (7) low to moderate topographic relief, allowing free movement of the water table but a minimum of erosion; and (8) long quiet periods in earth history. Assuming that all of these factors are operating to a greater or less degree, it seems that the one that affects most the physical character of the resulting bauxite or laterite deposits is the chemical and mineralogical composition of the rocks that by their decay yield the bauxite deposits. This factor is used in the classification followed in this paper. In the process of weathering of ordinary silicate and carbonate rocks of the earth's crust, whether of igneous or sedimentary origin, it is the minerals of the alkalies that yield most readily to attack. The alkaline earth compounds also offer no great resistance, particularly the carbonates. Thus, among the rock-forming elements, those producing the most insoluble compounds are aluminum, iron, and silicon, together with certain ones of less importance, such as titanium, manganese, and phosphorus. In normal weathering processes such as prevail in temperate regions, the common minerals of rock decay are

Jan 1, 1952

By E. H. Jr. Crabtree

THE productive area of asphalt-bearing sandstone in Missouri is near the Missouri-Kansas state line near Nevada, the county seat of Vernon County about 100 miles south of Kansas City. While produc-tion thus far has been confined to Vernon and Barton counties, there are known deposits in adjacent counties. The area is served by four rail-roads: the Missouri Pacific, the Kansas City Southern, the Missouri-Kansas & Texas, and the St. Louis & San Francisco. The plant of the Reliance Rock Asphalt Corporation is in Vernon County, about 5 miles west of Nevada, at Ellis, a flag station on the Missouri, Kansas & Texas Railroad. A siding has been built to the plant so that the finished product can be loaded directly into railroad cars. The property consists of a lease of 240 acres in one block. All portions of the property not required for quarrying or processing the asphalt-bearing sandstone are used for farming by the fee owner. The entire tract is very flat so that there are no transportation difficulties from quarry to plant.

Jan 1, 1935

By J. PARKCEH CHANNING

Discussion of the paper of Lewis T. Wright, presented at the New Haven meeting, February, 1909 (Trans., xl., 492 to 495). J. PARKE CHANNING, New York, N. Y. (communication to the Secretary*):-Mr. Wright, in his introductory paragraph, says: " It is commonly believed by metallurgists that in copper-smelting, the copper in the slags, which is irreducible by continued smelting, is retained in the form of 'prills' of matte." On a recent visit to Greenwood, B. C., I was discussing with J. E. McAllister, the general manager of the British Columbia Copper Co., and the former metallurgist of the Tennessee Copper Co., this very question; and he held strongly to the idea that the copper in slag was in two forms-one portion contained in occluded matte and the other as an oxide. He believed that this same rule would apply to the silver in the slag. From my experience I am strongly inclined to agree with Mr. McAllister; and it appears quite reasonable that in furnaces treating oxidized copper-ores, and to a less degree in furnaces treating sulphide ores, there is always bound to be present a certain amount of copper oxide and silver oxide, which will behave like any base and get into the slag as such. We all know that in Arizona, in the early days, when it was customary to produce black copper, because the ores were nearly all oxidized or carbonates, and sulphur was scarce, the slags as a rule carried 2.5 per cent. of copper and seldom ran less than 1.5 per cent. of copper. The economic point was determined by the extra coke necessary to produce the reducing action. In connection with the extra saving in copper, Arthur L. Walker, now professor of metallurgy at Columbia University, and formerly general manager of the Old Dominion Copper Mining Co., at Globe, told me that with coke at $60 per ton it never paid him to make slags containing less than 2.5 per cent. of copper. *Received Oct. 8, 1909.

Feb 1, 1911

By Benjamin Talbot

The problem of segregation and cavities in steel ingots is a subject which has given and is still giving metallurgists, engineers, and operators matter for serious consideration. This question has come more into prominence lately in the United States, due largely to the desire of railroad engineers to secure a better rail than they have obtained ill the past, as the service they demand is increasing in severity; and no doubt manufacturers will be able to meet what is required of them. The rails here are as good as those made in other countries, but the conditions of service and the extremes of climate are more Revere and consequently more breakages occur. Various reasons have been advanced to explain why rails may not be as good in quality to-day as in the past. Some engineers consider that modern methods of manufacturing, designed chiefly to obtain large output, tend to reduce the standard of excellence of more deliberate methods. Others think that 4-ton ingots are worse than those of 2 tons. Again, it is stated that the 100-ton heat in one ladle is too large, and is a step in the wrong direction in casting. My experience upon the question of the size of the ingot is that in rolling rails of from 85-to 100-lb. sections, the range of ingot is only practically such that the difference in the size does not help in the question of segregation, cavities, or blow-holes. I call attention to two ingots from work done at Pencoyd, Pa., 16 years ago. These ingots were bottom-poured, cast at the same time from the same center-runner, the one being 20 by 24 in. and the other 13 by 16 in. in size. The steel was acid open-hearth, and contained C, 0.43; P, 0.062; S, 0.069 per cent. At the same place in each ingot where seg-

Jan 1, 1914

Correspondent. Must be able, by virtue of, connection, to forward; daily ands weekly, reports, outlining, conditions affecting economics of. industries, particularly the metallurgical, and chemical, industries. New. York, City. R-1982. Sales Lubrication. Engineer. Preferably with experience, as chief marines engineer familiar with internal-combustion; engines and, with, automobile trade. Must be good salesman, of goody appearance and be able to meet people. Middle West. Salary $27.00: to start. R71984.

Jan 12, 1919

By F. R. Brotzen, A. R. Troiano, E. L. Harmon

Precipitation processes leading to drastic property changes are a frequent occurrence in titanium alloys containing large amounts of the retained high temperature P phase. In order to establish the kinetics and nature of these precipitation processes, a series of Ti-V alloys was studied. Time-temperature-transformation diqgrams were obtained for 12.5 and 15 pct V-Ti alloys. These diagrams consisted of two intersecting C-shaped curves: one in the high temperature region for the euilibrium transformation P +u+P, and another at lower temperatures depicting the formation of the meta-stable transition phase, o. Presence of the transition phase retarded the precipitation of the equilibrium a phase. Deformation of retained P resulted in the formation of the o phase. Reversion and retrogression phenomena of the transition phase were observed. A negative temperature coefficient of resistance was found in quenched alloys containing from 15 to 20 pct V. CERTAIN titanium-base alloys can be heat treated to produce appreciable changes in properties. For example, remarkably high hardness values may be obtained by aging or isothermal quenching treatments. Most of the information available to date on the hardening of titanium-base alloys has been systematized recently in an article by L. D. Jaffe.' It was pointed out by that author that the hardening was the result of the decomposition of the retained j3 phase to the equilibrium constituents, a and p, and that this decomposition had many of the characteristics of an age-hardening reaction. Recent work by Frost et al.' 3 has contributed much to the fundamental understanding of the hardening mechanism in titanium-base systems. These authors established the presence of a transition phase in the transformation from j3 to a + j3, which they designated o. The transition phase, in their opinion, was at least partially responsible for the hardening and embrittling effects which accompanied low temperature aging. The present investigation of the mechanism and kinetics of the hardening reaction was carried out for the Ti-V system. Ti-V alloys were ideally suited for a study of the decomposition of j3, since age hardening was known to occur readily in this system." Moreover, no intermetallic compounds occur in this system, Fig. 1, thus simplifying the interpretation of the results. Material and Procedure Alloys containing 12.5 and 15 pct V were prepared by Battelle Memorial Institute from iodide titanium furnished by Watertown Arsenal and vanadium of 99.8 pct purity. Ingots of 8 Ib each were prepared by arc melting in an inert atmosphere with a tungsten electrode and water-cooled copper crucible. Each of the ingots was melted once, forged at 1600°, and rolled at 1400°F. Following this, the ingots were remelted, forged, and then rolled to % in. sq bars, which were subsequently grit blasted, pickled, and wire brushed. Another set of alloys containing nominally 17.5 and 20 pct V was produced by the Research Div., New York University. These alloys were arc melted in an inert atmosphere in lots of 20 g each. Heat-Treating Procedure: Whenever feasible, specimens were heat treated in high vacuum resistance furnaces at pressures below 5x10." mm of Hg. Aging and isothermal quenching treatments were generally carried out in salt baths. Specimens were not attacked by the salt, provided the tempera-

Jan 1, 1956

By P. Ramachandrarao, T. R. Anantharaman

EVER since the technique of quenching metals and alloys from the melt (splat cooling) was perfected a decade ago, it has been recognized that the grain size of products solidified by this technique may be extremely small.' The further observation that fcc metals quenched from the liquid state contain very few dislocations has led to the inference2 that metals are subjected to negligible or no stresses during the rapid solidification characteristic of the "gun" or "piston-and-anvil" technique. Evidence for the incidence of appreciable densities of stacking faults has, however, been obtained in case of some splat-cooled fcc and hcp alloys,3 although not for pure metals. In the light of these earlier observations it was considered desirable to study X-ray line-broadening effects, if any, in fcc metals rapidly cooled from the melt. In the present work pure silver (>99.99 pct), aluminum (>99.99 pct) and lead (>99.9 pct) were quenched from the liquid state from temperatures about 50°C above the melting point by the "gun technique" and the resulting foils were subjected to X-ray examination in a Philips Diffractometer. The quenched foils (up to -10 u thick) did not generally stick to the substrate surface and could be easily transferred to the Diffractometer without introducing any plastic deformation. The profiles of the first five reflections from the foils were recorded in each case with Cu Ka, radiation at the slowest available scanning speed of 1/8 deg per min. To correct for instrumental broadening, profiles were also recorded from the metals annealed in vacuo at suitable temperatures. The integral breadths of the X-ray reflections were arrived at by a procedure described earlier.' There was a distinct suggestion of preferred orientation in the recorded intensities of reflections from aluminum and lead foils. Such an effect was not observed in case of silver. In addition, the integral breadths of X-ray reflections from splat-cooled aluminum and lead were not significantly different from those recorded for the annealed metals. The analysis was therefore continued only for silver where the X-ray line broadening was appreciable. The pure diffraction broadening, B, was evaluated for each X-ray reflection (hkl) from silver from the observed, B, and instrumental, b, breadths with the aid of each of the three equations due to Scherrer,5 Anantharaman and Christian,6 and Warren and Biscoe,7 respectively: Bs= B-b BAC=B- b2/B Table I gives the values of particle size, 71, the lattice strain, E, arrived at by the use of the following well-known relations and on the assumption that all observed diffraction broadening could be attributed to lattice strain or particle size, respectively: E = 1/4 cos ? n= B cos ? where A is the wavelength of X-radiation and 0 is the Bragg angle. As no significant peak shifts or asymmetry could be detected in the profiles from the foils, the possibility of any significant contribution due to twins or stacking faults was ruled out. The absence of faults is by no means surprising since pure silver is known to develop stacking faults only on severe deformation and the stacking fault densities recorded so far for even silver filings have been extremely low.' The very low values for percentage mean deviation from the mean value for the particle size in Table I strongly suggest that all observed broadening in splat-cooled silver can be attributed only to small particle size. This conclusion receives further support from the lowest mean deviation recorded for data computed from the Scherrer equation based on Cauchy profiles that are considered characteristic of particle size broadening. Further analysis for separation of particle size and lattice strain effects was considered unnecessary in view of the very large mean deviations obtained for strain values and also the earlier results suggesting absence of even detectable strain in metals and alloys quenched from the melt. It is to be stressed in this connection that the particles are actually grains and not cells formed by walls of high dislocation density usually encountered in deformed samples. As such, the absence of strains is not surprising. The present results are probably the first to record X-ray line broadening due only to small particle

Jan 1, 1970

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By J. Weijdema, D. N. Dietz

In the conventional underground combustion process (dry combustion) much heat is left behind in the swept formation and goes to rva.rte. Econonmy can be improved by heat recuperation through water injection. This is most advantageous if done at the earliest opportunity before much heat is dissiputed to cap and base rock. Water injected simultaneously with the air will flash to superheated steam, which passes through the combustion front together with the nitrogen from the air. A condensation front traveling up to three times as fast as the combustion front drives out the oil. In this type of wet combustion, the water evaporates before it reaches the combustion zone. The evaporation front travels more slowly than the combustion zone. If so much water is injected that the evaporation front overrun the combustion front, combustion in that spot will be quenched and some unburned fuel will be left behind. Air reacts with the oil farther down-stream where steam temperatures occur; at steam temperature, the air reacts rapidly with the oil. Velocity of the combustion front is increased thereby and is governed essentially by the water-injection rate. In the extreme case of high water-injection rate, a short heat wave of constant length is driven through the formation by water injection. Once this wave has been established, no more heat need be generated than that required to make up the heat losses from the short heat wave; a relatively low rate of air injection will suffice. The feasibility of partially quenched combustion has been confirmed in tube experiments. A heat wave at steam temperature is observed. Chemical analyses of flue gas indicate preferential burning of hydrogen while a carbonaceous residue is left in the formation. Introduction A disadvantage of so-called dry in situ combustion is that air-compression costs are rather high. An air consumption of about 400 std cu m/cu m (400 scf/cu ft) of formation swept is an accepted figure. This high consumption is mostly wasted since much heat is left behind in the depleted oil sand. Methods were investigated for recuperating as much as possible of the heat left behind. This paper deals only with basic principles and is confined mainly to one-dimen- sional flow without lateral heat losses; experiments were conducted in relatively narrow, well insulated tubes. If some water is injected with the air, it will turn to superheated steam in an evaporation front, which should travel behind the combustion front. The steam having passed the combustion front causes a steam drive by a condensation front that can travel faster than the combustion front. The latter needs to travel only part of the distance covered by the oil-displacing condensation front, and thus consumes less air. The water-air ratio would seem limited to that at which cold water overruns the combustion. This limitation was deliberately exceeded considerably in theory and experiments. It was found that combustion is then indeed quenched, but only locally. Farther downstream, the oxygen finds residual oil at steam temperature, which is suficiently high to ensure rapid oxidation. Thus, the combustion front uses only part of the available fuel because it is chased through the formation faster than its normal velocity. No heat is left behind. This new process is called "partially quenched combustion". At the upper limit of the water-air ratio, a small heat slug is moved through the formation by the flow of water and steam. Only a small flow of air is needed since it has only to generate sufficient heat to make up for the lateral heat losses of the short heat slug. Theory Although many factors complicate underground combustion, the processes will be presented in their simplest form. For this reason, one-dimensional flow without lateral heat losses is assumed. Heat conduction in the direction of flow also is disregarded. Under these conditions, dry combustion causes very high temperatures. The heat-carrying capacity of the gas stream is small. Heat generated by oxidation of a residual oil saturation is retained in the sand. The available fuel determines the air requirement and the temperature obtained. Accepting the often-mentioned air consumption of 400 std cu m/cu m (400 scf/cu ft) formation, we calculate a temperature of the swept sand of 1,200C (2,192F) (Fig, I). If water is injected at a modest rate with the air, it will flash to superheated steam upon contact with the heated sand. One cu m (35.31 cu ft) of hot formation will evaporate about 0.5 cu m (17.66 cu ft) of water, and thereafter will accommodate (at an estimated 0.80 saturation and an assumed 0.40 porosity) another 0.3 cu m (10.59 cu ft) of water in cold condition. As long as less than 0.5 + 0.3 = 0.8 cu m (28.25 cu ft) of water is injected for every 400 std cu m (14,125 scf) of air (water-

Jan 1, 1969

By H. J. Rahilly

MINE FIRES, in the Butte District, have been a source of trouble and expense for the past thirty years, for while the actual fire area in most of the mines has been comparatively small, the handling of the gas has generally been a much larger problem than the actual putting out of the fire. The chief causes of these fires have been: Defective electrical equipment, incendiarism or carelessness, and spontaneous combustion. While fires from the first two causes have been numerous, they have generally been discovered and extinguished before they became very serious. Spontaneous combustion has been the cause of most of the large fires. Sufficient heat has been generated by ground movement, high rock temperatures, and decomposition to set fire to inflammable materials (tarred ropes, canvas, dry timber, manure, and hay) left in the gobs some years ago. Also, the heat resulting from the oxidation of the fine broken sulfide ore is sometimes sufficient to set fire to the timbers. In 1906, a fire was discovered on the 1100-ft. level of the Minnie Healy mine about 400 ft. (122 m.) west of the Minnie Healy shaft, which presumably originated, in one of the upper levels, from spontaneous combustion. The fire was walled off by concrete bulkheads and a pillar of ground 100 ft. (30 m.) thick was left below and mining resumed underneath. During subsequent operations, this pillar became cracked and broken and the fire passed into the new workings. It travelled downward and spread rapidly until, in 1917, it had become necessary to wall off portions of the Tramway, Leonard, and West Colusa mines on the 1300, 1400, 1500, 1600, 1800, 1900, and 2000-ft. levels, and the top of the 2200-ft. raises were sealed. The fire area now consists roughly of a block 1000 by 1200 ft. and from the 600-ft. to the 2200-ft. level. This block is composed largely of a series of parallel northwest-southeast nearly vertical veins and stringers that form a large orebody, with no well-defined walls but badly fractured and faulted, and known locally as "Horsetail Ore." These veins, or orebodies, are mined by the square-set or the rill method.

Jan 2, 1922

The Institute assembled in the room of the Board of Trade, Mercantile Library Building, on Tuesday evening, May 20th, at 8 o'clock P.M, Hon. W. D. Kelley made an address of welcome to the Institute, which was responded to by President Raymond. The Council reported, through the President, that the Institute had during' the past year, held three meetings, in New York, Pittsburgh, and Boston. Thirty-nine papers of great professional value had been read, and sixty-nine members and twenty-four associates added to the Institute. The finances of the Institute were in good condition, the report of the Treasurer, Mr. T. D. Rand, showing a balance on hand of $1569.74. The report was accepted. Prof. L. Gruner, of Paris, France, and Prof. Peter von Tunner, of Leoben, Austria, having been proposed by ten members of the Institute, and approved by the Council, were unanimously elected honorary members. The Council reported the names of the following gentlemen, with recommendation for election as members or associates. They were unanimously elected. *Barker, Prof. G. F.,.....Philadelphia, Pa. Chalfant, John W.,.....Pittsburgh, Pa. *Crawford, John J.,.....Philadelphia, Pa. *Crusius, O. H.,.Columbus, Ohio. Dibble, Theo. Hoyt,.....Pottsville, Pa. Everson, John,. Pittsburgh, Pa. Field, Robt. P.,.Philadelphia, Pa. *Fisher, F. A.,.Bristol, Tenn. *Fleming, W. E.,.Pioche, Nev. *Harden, E. B ,..Philadelphia, Pa. *Harding, G. E.,.New York. Hartshorne, J.,..'Philadelphia, Pa. Haupt, H., Jr.,.Philadelphia, Pa.

AT the meeting of the Board of Directors held on June 25, 1926, and in response to numerous in-dividual suggestions for changes, a committee on Re-vision of the Constitution and By-Laws of the Insti-tute was appointed, consisting of C. F. Rand, Archi-bald Douglas and H. Foster Bain. Various confer-ences were held, much correspondence conducted and a preliminary draft was prepared. It proved imprac-ticable to complete the work in time to submit the matter to the membership for approval or disapproval at the annual meeting in 1927, and the Committee was continued with instructions to prepare a report as a basis of action in 1928. After Mr. Rand's death George Otis Smith was appointed in his place and the tentative draft herewith submitted has been pre-pared in its present form by Messrs. Smith, Douglas and Bain, though not differing in any material mat-ter from an earlier draft approved by Mr. Rand. In preparing this the Committee has kept in mind primarily the desirability of simplification and of making the By-Laws conform to the actual practice of the Institute as worked out through experience. The Constitution and By-Laws adopted in 1912, and which with minor amendments only still govern the Insti-tute, are full of specific provisions regarding pro-cedure; such as that laid down for guidance of the Papers and Publications Committee. Many of these have proved unworkable and in practice have not been always strictly followed. It now seems wise to write into the Constitution and By-Laws only the general fun-damental principles to he followed and to provide for such easy change in methods of following them out as will permit efficient conduct of the business. It is this thought that has guided the Committee in rewrit-ing many of the sections. With this in view also the Constitution, as such, has been shortened to the brief-est feasible statement of fundamentals. All matters relating to means of making these principles effec-tive have been put into the By-Laws or in the hands of committees whose work is subject to control and whose rules are subject to approval or disapproval by the Board of Directors. Many suggestions for changes have come to the Committee that have not been incorporated in this draft. Some of these are in themselves excellent but have not been incorporated here because the Commit-tee discovered no sentiment for them such as would be likely to secure their approval, or found them out of harmony with the general plan followed herein.

Jan 9, 1927

By H. J. Rahilly

Mine fires, in the Butte district, have been a source of trouble and expense for the past thirty years, for while the actual fire area in most of the mines has been comparatively small, the handling of the gas has generally been a much larger problem than the actual putting out of the fire. The chief causes of these fires have been: Defective electrical equipment, incendiarism or carelessness, and spontaneous combustion. While fires from the first two causes have been numerous, they have generally been discovered and extinguished before they became very serious. Spontaneous combustion has been the cause of most of the large fires. Sufficient heat has been generated by ground movement, high rock temperatures, and decomposition to set fire to inflammable materials (tarred ropes, canvas, dry timber, manure, and hay) left in the gobs some years ago. Also, the heat resulting from the oxidation of the fine broken sulfide ore is sometimes sufficient to set fire to the timbers. In 1906, a fire was discovered on the 1100-ft. level of the Minnie Healy mine about 400 ft. (122 m.) west of the Minnie Healy shaft, which presumably originated, in one of the upper levels, from spontaneous combustion. The fire was walled off by concrete bulkheads and a pillar of ground 100 ft. (30 m.) thick was left below and mining resumed underneath. During subsequent operations, this pillar became cracked and broken and the fire passed into the new workings. It travelled downward and spread rapidly until, in 1917, it had become necessary to wall off portions of the Tramway, Leonard, and West Colusa mines on the 1300, 1400, 1500, 1600, 1800, 1900, and 2000-ft. levels, and the tops of the 2200-ft. raises were sealed. The fire area now consists roughly of a block 1000 by 1200 ft. and from the 600-ft. to the 2200-ft. level. This block is composed largely of a series of parallel northwest-southeast nearly vertical veins and stringers that form a large orebody, with no well-defined walls but badly fractured and faulted, and known locally as "horsetail ore." These veins, or orebodies, are mined by the square-set or the rill method.

Jan 1, 1923

By H. J. Rahilly

Mine fires, in the Butte district, have been a source of trouble and expense for the past thirty years, for while the actual fire area in most of the mines has been comparatively small, the handling of the gas has generally been a much larger problem than the actual putting out of the fire. The chief causes of these fires have been: Defective electrical equipment, incendiarism or carelessness, and spontaneous combustion. While fires from the first two causes have been numerous, they have generally been discovered and extinguished before they became very serious. Spontaneous combustion has been the cause of most of the large fires. Sufficient heat has been generated by ground movement, high rock temperatures, and decomposition to set fire to inflammable materials (tarred ropes, canvas, dry timber, manure, and hay) left in the gobs some years ago. Also, the heat resulting from the oxidation of the fine broken sulfide ore is sometimes sufficient to set fire to the timbers. In 1906, a fire was discovered on the 1100-ft. level of the Minnie Healy mine about 400 ft. (122 m.) west of the Minnie Healy shaft, which presumably originated, in one of the upper levels, from spontaneous combustion. The fire was walled off by concrete bulkheads and a pillar of ground 100 ft. (30 m.) thick was left below and mining resumed underneath. During subsequent operations, this pillar became cracked and broken and the fire passed into the new workings. It travelled downward and spread rapidly until, in 1917, it had become necessary to wall off portions of the Tramway, Leonard, and West Colusa mines on the 1300, 1400, 1500, 1600, 1800, 1900, and 2000-ft. levels, and the tops of the 2200-ft. raises were sealed. The fire area now consists roughly of a block 1000 by 1200 ft. and from the 600-ft. to the 2200-ft. level. This block is composed largely of a series of parallel northwest-southeast nearly vertical veins and stringers that form a large orebody, with no well-defined walls but badly fractured and faulted, and known locally as "horsetail ore." These veins, or orebodies, are mined by the square-set or the rill method.

Jan 1, 1923