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By G. M. Lee

SEVERAL improvements have been made in Granby smelting practice since the company abandoned the direct smelting of raw ore in the blast furnaces in June, 1927, in favor of sintered concentrate. These improvements have been made in several fields, but the most novel and outstanding change was the development of a process of concentrating most of the gold, and a somewhat smaller fraction of the silver present, in a small portion of the blister copper produced. The practice of making "copper bottoms" is usually associated with the reverberatory smelting of copper ores containing high percentages of impurities, or of copper matte high in precious metals. It has for its object, in the one case, the production of a major part of the copper relatively free from impurities and, in the other case, the production of a small per¬centage of the copper carrying the major part of the precious metals. Although the blister copper produced at the Anyox plant of the Granby company is remarkably free from deleterious impurities and normally contains no great amount of precious metals, certain economic considerations made it advisable to concentrate the existing precious metals into a relatively small percentage of the blister copper produced. The process devised took advantage of principles and reactions of the usual bottoms processes, but was carried out in the converters instead of in a reverberatory furnace.

Jan 1, 1935

By J. F. Mitchell, R. Bainbridge, E. A. Melvin

IN the fall of 1953, The Consolidated Mining and Smelting Co. of Canada Ltd. put into operation a completely new and modern plant for sintering the rather complex assortment of materials which comprise the feed to the Lead Smelter at Trail, British Columbia. This Lead Smelter is one section of an integrated metallurgical plant producing lead, zinc, silver, gold, cadmium and other metals. Since most of the incoming lead concentrate contains appreci- able zinc values, and most of the zinc concentrate similarly contains appreciable lead values, the cross-routing of residues or tails from the respective lead and zinc plants offers obvious advantages in recovery of metals, and has been practiced for many years. A disparity has existed, however, between the output of zinc plant residue and the capacity of the Lead Smelter to treat it, with the result that over the years a stock-pile of residue had been accumulating, and by the end of World War II had reached the formidable total of half a million tons. To treat this stock-pile, in addition to all current zinc plant residues and, of course, the regular quota of lead concentrates, became a prime objective of the Lead Smelter following World War 11. As zinc plant residue plays an important part in the operations to be discussed in this paper, some consideration of its

Jan 1, 1958

By RUSSELL C. FLEMING

GILSONITE is a brilliant black, tarry-like bitumen, classed technically with glance pitch and graharnite as an asphaltite. As found it is brittle, breaking much like ice, and has a conchoidal fracture. Purest forms are used in the manufacture of paints, varnishes, electrical irisulatiorl, and inks for rotogravure; molded articles such as switch handles, telephone mouthpieces, and but- tons are made from the intermediate grades, and the poorer grades are used for the saturation of felt. According to the U. S. Bureau of Mines figures, production grew from about 4000 tons mined in 1904 to 55,000 tons in 1929. This asphaltic substance is found only in the Uintah basin in northeastern Utah, in veins over a wide area. Veins in the vicinity of Fort nuchesne were first discovered about 18G2, on what was then the Uintah Indian reservation, and the vein matter was originally called Uintaite because of that fact, In the early days, S. H. Gilson. of Salt Lake City, was so persistent and zealous in his efforts to develop the deposits and find a market that the name gilsonite was given to the material. Later, the wider and more renowned wins near Wayson and Dragon, in extreme eastern Utah, became the main supply.

Jan 1, 1932

By R. B. Mears, G. F. Sagar, R. H. Brown

There are well recognized procedures for determining the various tensile, fatigue, and other mechanical properties of the common structural materials. This makes it possible for engineers to design structures of various materials which have adequate initial strength to stand the stresses to which they are subjected in service. There is also considerable general information about protective measures suitable for protecting the usual structural materials from the effects of ordinary environments. However, often insufficient quantitative information is available on the combined effects of stress and corrosion to permit the designer satisfactorily to appraise the structure from the stress-corrosion standpoint. This situation is further complicated by the fact that the stresses causing stress¬corrosion failures are usually not the design stresses but rather the residual forming and assembly stresses which are generally of unknown magnitudes. Thus, tests which will rapidly evaluate the susceptibility of materials to stress-cor¬rosion failures are extremely useful. Of particular value are tests which can be applied to built-up structures as well as to simple specimens, since, as mentioned above, residual stresses often are caused by fabricating procedures and assembly operations. The present paper contains

Jan 1, 1945

By L. R. Smith

BUTANE OPERATED drilling rigs are a recent innovation in the petroleum industry, so extensive data on their operation are not available. However, experience indicates that, within limitations, as much can he accomplished with butane as with steam, at a decided reduction .in expense of installation and cost of operation. Commercial butane is a liquid motor fuel similar to gasoline, but much more volatile, so that it has to be stored under pressure. At 10° F. it is liquid at atmospheric pressure, but at 100° it has a pressure of 70 lb. or more. As soon as the pressure is reduced, it turns to vapor and in that state is far more easily mixed with the air necessary for combustion. Butane occurs as a by-product in the absorption process of natural gasoline extraction from casing-head gas. The product has been used to some extent 10 raise the octane value of gasoline. However, because of its volatile nature, such admixture is stable only to a limited degree. Attempts also have been made to introduce the product in a gaseous form into oil- hearing formations in repressuring work. It has, however, until recently, for the most part been wasted.

Jan 1, 1937

By A. Keith Brewer

RECENT advances in the fields of chemistry, biology, and metallurgy have confronted the analytical chemist with an entirely new set of problems. Development of plastics and synthetics has brought about a need, not only for adequate methods for their analysis but also for the various raw materials entering into their manufacture. The remarkable advance made in biochemical and agricultural research resulting from the use of isotopes as tracers or "tagged atoms" has established the necessity for the development of methods for the concentration of natural isotopes and for a means for their analysis. Similarly the advent of new and complex alloys calls for accurate analytical methods. Fortunately the analytical chemist has been able to meet some of these new demands by adapting to his purposes an instrument which has long been the most exclusive toy of the physicists. Solubility and the chemical properties of the atoms, which have always served as the basis for chemical analysis, do not enter into this new technique. Instead, momentum, defined as mass times velocity, is utilized as the means for the separation of atoms or mass groups.

Jan 1, 1946

By Clyde Williams

IF you would allow me some liberties, I would restate the title of this talk as "Scientific Research, Our Greatest Resource," because that title would represent more clearly a present-day conception of the metals and minerals situation. It is a subject worthy of careful consideration. Canada and the United States are so similar and interdependent in their national economies that, in the following discussion, examples of conditions in the United States may be interpreted to apply to Canada as well. Moreover, it is a striking fact that the per capita value of mineral production in Canada and the United States in 1940 was almost the same. Therefore, in the consideration of this subject, I have made no attempt to differentiate between the two countries. Consumption of the world's mineral resources in the last few decades. and particularly during World War II, has been so enormous as to require some form of magic to ensure the continued progress of civilization in the face of a diminishing supply of these resources which are so critically essential. As C. K. Leith pointed out, in 1941, indus-

Jan 1, 1947

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By J. H. Wernick

IN a study of the rate of decomposition of %-in. cubes of limestone, dolomitic limestone, and dolomite in a sweeping nitrogen atmosphere, Joseph, Beatty, and Bitsianes' found that the zone of calcination advanced at substantially a constant rate at a given temperature. The purpose of this paper is to show that their data indicate at least two processes occurring when the above carbonates decompose. It is suggested that there are two processes occurring consecutively, one the limiting process in a given temperature range and the other the limiting process over another temperature range. The data of Joseph and co-workers have been extended by use of the Arrhenius equation, Eq. 1, a relation beween the velocity constant k of a reaction and the absolute temperature T. d In k A ' dT Rr2 A is the activation energy in calories per mol (additional energy that must be added for an average molecule to react), and R is equal to 1.986 cal

Jan 1, 1955

By J. Brian Eby

The Gulf Coast of southern Louisiana during the year of 1940 was subjected to an extensive exploration and development campaign, as a result of which 16 oil fields and about 38 new producing sands were found. Although this record of discovery appears in keeping with the rate of 1939 actually in amount of new proven reserves, it may fall short of that of the previous year. Only five or six of the discoveries rated as first-class or important fields at the close of the year. The most prominent new fields opened during the year were Neale field in Beaure-gard Parish, the West Cote Blanche field in St. Mary Parish, the Stella field and the West Bay field in Plaquemines Parish, and the Lake Salvador field in St. Charles Parish. There were many important oil-sand discoveries in proven fields, such as in the Bayou Perot field, the Golden Meadows field, the Iowa field, West Lake Verrett field, and the Venice field. During the year, 1047 weUs were drilled in southern Louisiana, of which 768 were completed as oil-producing wells, 17 as gas wells and 262 as dry holes. The Neale field in northwest Beauregard Parish is considered one of the most important discoveries of the year. The f~eld centers around the north half of sec. 26, 'Y.3 S., R.I I W., just north of the town of Neale. It was discovered by the Atlantic Refining Co., using reflection seismograph to locate the structure. Production was found in the second well drilled in the Wilcox sand on the downthrown side of a fault. The structure is known as the "Tepetate" type, being similar to that of the well-known Tepetate field. There were 12 oil wells and 3 dry holes drilled during the year. The Wilcox sand in this field occurs between 8350 and 8400 ft. and averages 30 ft. in thickness. The West Cote Blanche Bay field, in West Cote Blanche Bay, St. Mary Parish, is a 1940 discovery by the Texas Company, credited to reflection seismograph exploration. The oil is from two sands occurring at 3110 to 3140 ft. and from 4950 to 5020 it. Four wells were drilled during the year, three oil wells and one dry hole. The deepest hole drilled reached 9491 ft. without encountering salt or dome material. In Plaquemines Parish, south of New Orleans, the California company has a new field known as the Stella field. The sand was found at a depth of 7485 ft., and 5 ft. of perforations made a well capable of producing 486 bbl. of oil in 24 hr. through a 9.is-in. choke. The oil is 42" gravity. The discovery well was drilled to a total depth of 10,258 ft. and other producing sands were indicated. A good field appears assured, although only one well was completed within the year. The Lake Salvador field, in the center of Lake Salvador, St. Charles Parish, gives promise of being one of the most important discoveries of the year. The discovery well was perforated at 9775 to 9800 ft. making 850 bbl. of 33.7° gravity oil daily through a 1/4-in. choke. Three wells were completed in 1940 but few details have as yet been made available.he Gulf Oil Corporation apparently has a good field in its wildcat discovery in West Bay, Plaquemines Parish. This well found

Jan 1, 1941

By J. Brian Eby

The Gulf Coast of southern Louisiana during the year of 1940 was subjected to an extensive exploration and development campaign, as a result of which 16 oil fields and about 38 new producing sands were found. Although this record of discovery appears in keeping with the rate of 1939 actually in amount of new proven reserves, it may fall short of that of the previous year. Only five or six of the discoveries rated as first-class or important fields at the close of the year. The most prominent new fields opened during the year were Neale field in Beaure-gard Parish, the West Cote Blanche field in St. Mary Parish, the Stella field and the West Bay field in Plaquemines Parish, and the Lake Salvador field in St. Charles Parish. There were many important oil-sand discoveries in proven fields, such as in the Bayou Perot field, the Golden Meadows field, the Iowa field, West Lake Verrett field, and the Venice field. During the year, 1047 weUs were drilled in southern Louisiana, of which 768 were completed as oil-producing wells, 17 as gas wells and 262 as dry holes. The Neale field in northwest Beauregard Parish is considered one of the most important discoveries of the year. The f~eld centers around the north half of sec. 26, 'Y.3 S., R.I I W., just north of the town of Neale. It was discovered by the Atlantic Refining Co., using reflection seismograph to locate the structure. Production was found in the second well drilled in the Wilcox sand on the downthrown side of a fault. The structure is known as the "Tepetate" type, being similar to that of the well-known Tepetate field. There were 12 oil wells and 3 dry holes drilled during the year. The Wilcox sand in this field occurs between 8350 and 8400 ft. and averages 30 ft. in thickness. The West Cote Blanche Bay field, in West Cote Blanche Bay, St. Mary Parish, is a 1940 discovery by the Texas Company, credited to reflection seismograph exploration. The oil is from two sands occurring at 3110 to 3140 ft. and from 4950 to 5020 it. Four wells were drilled during the year, three oil wells and one dry hole. The deepest hole drilled reached 9491 ft. without encountering salt or dome material. In Plaquemines Parish, south of New Orleans, the California company has a new field known as the Stella field. The sand was found at a depth of 7485 ft., and 5 ft. of perforations made a well capable of producing 486 bbl. of oil in 24 hr. through a 9.is-in. choke. The oil is 42" gravity. The discovery well was drilled to a total depth of 10,258 ft. and other producing sands were indicated. A good field appears assured, although only one well was completed within the year. The Lake Salvador field, in the center of Lake Salvador, St. Charles Parish, gives promise of being one of the most important discoveries of the year. The discovery well was perforated at 9775 to 9800 ft. making 850 bbl. of 33.7° gravity oil daily through a 1/4-in. choke. Three wells were completed in 1940 but few details have as yet been made available.he Gulf Oil Corporation apparently has a good field in its wildcat discovery in West Bay, Plaquemines Parish. This well found

Jan 1, 1941

By M. H. HARRINOTON

THE Transactions of the Institute afford abundant evidence of the general recognition by mining engineers of the importance of a safety-lamp which will not only give warning of the presence of fire-damp, but will also indicate the proportion in which it is present.' Mining-men are only too familiar with the frequent and sudden changes that constantly occur at the working-face of a gaseous mine. Nothing illustrates more forcibly the pregnant condition of the strata enfolding the seam and the seam itself, than the fact that a circulation of perhaps 150,000 cu. ft. of air may contain 2 or even 3 per cent. of marsh-gas, representing a volume of from 3,000 to 4,000 cu. ft. of this gas pouring-out each minute from the natural strata into the mine-workings. It would, indeed, be strange if this great outflow of gas were always constant, and it creates no surprise that such earth-breathings, as they may be called, are spasmodic and irregular in their wane and flow. There are other causes that act to vary the gaseous condition of mine-air. Gas has a tendency, often very manifest in mine-workings and airways, to stratify and, at times, to travel long distances in veins or streams. It is common to catch and lose the gas in the lamp when making a test. At times two lamps, held side by side in an air current, will indicate different gaseous conditions of the passing air. When testing for gas, the lamp may suddenly fill with flame, in a mine-chamber, where a moment before a careful test showed the presence of but 1 per cent. of gas. It is sometimes remarked that there is little need of detecting a smaller percentage of gas than is revealed by the common

Jan 1, 1906

By Robert M. Weidenhammer

For years before the war, Coal had the reputation of being a sick industry. Currently it is operating at peak production and succeeding pretty well in keeping out of the red. But, says Mr. Weidenhammer, it will have a relapse as soon as the war ends unless (1) working capital can be built up; (2) it gets the support of the people and Congress; and (3) a truly long-range national fuel policy is formulated.

Jan 1, 1943

By Paul M. Tyler

HISTORICAL concepts of the economics of the glass-sand industry are changing rapidly. The greatly expanded demand for glass containers combined with higher freight rates on raw materials and manufactured products have induced a migration of glass factories toward densely populated centers and the creation of new standards of place value for sub- standard sand deposits. This migration has been facilitated by the construction of pipelines to bring cheaper natural gas and liquid fuel to large cities and may be further speeded by the adoption of modern mineral dressing methods to permit economical utilization of local raw materials. Our national resources of naturally high-grade 1 silica sand are abundant, but most of the best de- posits are situated so far from large centers of population that it now costs $3.00 to $5.00 a ton to carry the sand from the mine to the optimum site for a 1 factory making beverage bottles, scientific and electrical glassware, and miscellaneous blown and pressed ware for local markets. It follows that on the basis of freight savings alone it may be economical to use material from inferior deposits closer to the factory even though the f.o.b. cost of mining and treatment may be much high

Jan 1, 1950

By C. M. Brinckerhoff

Safety work in mining at the Andes Copper Mining Company, Potrerillos, Chile, is divided into three parts: (1) accident prevention, (2) fire prevention and protection, and (3) silicosis prevention and control. In the company's operations a steady campaign has been waged to reduce accidents and silicosis, and to prevent fires. In the following pages the safety record for the past twelve years will be examined and the methods explained by which the accident rate was reduced. Table 1 contains yearly data pertaining to the scale of the mining operations and the accident record. Block caving is used for all ore production and the tonnage mined has aver- aged 30,000 short tons per day for the past seven years. Table 2 classifies 44 fatal accidents which have occurred since 1935. The leading causes of accidental death are transportation of ore and use of explosives, followed in order by per- sons falling, falls of ground, and by asphyxiation. In the case of serious accidents, however, the greatest cause is falls of ground, followed, in turn, by ore

Jan 1, 1949

[A Editor's Note: Annual Reviews of various subjects and areas are found in February issues of Mining and Metallurgy and Mining Engineering. These Annual Reviews are not listed per se in the Index. Abating Stream Pollution in Anthracite Coal Fields. ME Mar 50 Abbadia San Salvatore mine, Italy. T178, 297 Abbott, C.E.: Limestone Mine in the Birmingham District. With Discussion. T129, 62 ABC Typifies Trend to Mechanized Mining and Coal Preparation. ME Dec 50 Abel, J.F.: Statistical Analysis of Tunnel Supporting Loads. T235, 288 Sulzbach, J. F., and Walker, D.K.: Ice Tunneling in Greenland. ME Jun 59 Aberfoyle tin mines, sphalerite, chalcopyrite, stannite, as intergrowths. T214, 1147 Abnormal Behavior of Some Ore Constituents and Their Effect on Blast Furnace Operation, The. T241, 1 Abrams, C.J.: Industry's Responsibility in Postwar Economy. M&M Mar 45 and Haley, D.F.: History of Crushing and Milling at Climax. M&M Jun 46]

Jan 1, 1972

By J. Armanet

THREE MINING colleges are maintained in France; the École Nationale Supérieure des Mines, of Paris; École Nationale Supérieure des Mines, of Saint Etienne; and the École Supérieure de la Metallurgie et des Mines at Nancy. Besides graduates of these schools, a few graduates of the École Centrale des Arts et MIanufactures and of the École Polytechnique are employed as ]nine managers or engineers; however, most of the latter have taken a graduate course at one of the mining schools.

Jan 1, 1939

?ADAIR, ARTHUR C., Corp 4th Co., 1st. Training Bat., 154th Depot Brigade. ADAMS, HENRY, Major: Chemical Warfare Service. ARLUCK, A. A Headquarters, 1st Corps of Artillery. ASKIN, THOMAS B. H Ensign. BANKS, H. R., 2d Lieut Canadian Engineers. BAYLESS, G. E. S Supply Dept. U. S. Submarine Base. BELL, L. R Co. C, 302d Engineers. BELLIS, ARTHUR E., Capt Ordnance Reserve Corps. I BIRRETT, HOWARD, Lieut., Aviation Section, U. S. Signal Corps, Ellington Field. BOISE, PAUL T 2d Regiment, 24th Squadron. ?BRADLEY, CLARENCE I Convois Automobile Section 585. BROWN, GEORGE M Co. G lot Engineer Replacement Regiment. BUCKINGHAM, ALBERT U. S. S. " Coronet," S. P. 194, Section Base No. 7. BURNS J. J Co. 1-B, E. R. O. T. C. BURT, Co. B, let Engineers Replacement Regiment. ||BYERS, WHEATON B., 2d Lieut Ordnance Dept. CANTON, WILLIAM R., Sgt Headquarters Co., 80th F. A. CARSON, JOSEPH A., Capt A.S. S. R. C.' CHAPMAN, LEWIS C. Corp 29th engineers. CHETNEY, P. C., 2d Lieut 15th Bat. Headquarters Co. CHEVRILLON Louis French Red Cross. CHIDESTER, W. B., 1st Lieut 24th Machine Gun Bat. CHURCH, JOHN L., Capt 308th Engineers. CLAGHORN, D. MONTGOMERY, 1st Lieut 45th Engineers. CLAQHORN, JAMES L., Lieut Aviation Section, Signal Corps. CLARKE, ALEXANDER F U. S. Naval Aviation Service. COMINS, WALDO H. Ca t 41st Co., 164th Depot Brigade. COOK, FREDERICK A., Capt., Engineer Reserve Corps, Asst. to Div. Engr. 79th Division. COOPER, CLAUDE H. Capt C. A. R. C., 50th Artillery. COPELAND, N. R., Lieut. ||CORBY H.. G., 1st Lieut Co. D, 109th Supply Train. CORSA, BEAN, Capt Co. D, 612th Engineers. CORTESE, EMILIO Italian Army. COULDREY PAUL S., Corp British Expeditionary Forces. || CRAGIN, RODNEY S Co. E, 115th Engineers. CURRIE, JOHN M., Ca t Royal Engineers. || CUTTING, G. W., 2d Lieut U. S. Reserves, Field Artillery. V DARRINGTON, PAUL N., 1st Lieut U. S. Infantry. DAVIS, ANGUS W., Lieut-Col British Expeditionary Forces. || DAVIS, THORNTON, 1st Lieut 13th Field Artillery. ELAND, FREDERICK A., Major Engineer Reserve Corps. DOUGLAS, JAMES $ American Red Cross. DOVE, D. R., Candidate 21st Training Battery, F. A. C. O. T. C. Dover JAMES J 6th Co. C. B. DOWS, DAVID,Capt Coast Artillery, Officers Reserve Corps. || DRAKE, M. 6., 2d Lieut Headquarters Co., 325th Infantry. I || EMMERSON, E. Roy British Navy. EVERIT, RICHARD STURTEVANT Heavy Artillery Officers' Training Camp.

Jan 1, 1923

By E. A. Gulbransen, W. S. Wysong

The behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance. The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotec-tive nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance studyl, 2 of the following problems: (I) the oxidation kinetics in the temperature range of 250°to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films; and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 2 50°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide Moo3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics: time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation. The general interpretation of many of these factors has been previously discussed. Literature The oxidation of molybdenum has not been studied critically. Although many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Gulbransen." Their results showed that Moo2 is the oxide which is stable in contact with the metallic substrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Moos is no longer observed, MoO2 being the only oxide found. Hagg and Magneli6 have shown from an X ray study that the a-phase, orthor-hombic Moo3 is stable up to 1050°C. Two other phases, ß and ß with compositions close to MoO2.90 are also obtained. The formula for the 0 phase is not given but that of the ß phase is defined as Mo9O26 The 0' phase is found to be built upon a monoclinic unit cell. A ?-phase is isolated from a preparation MoO2.75 heated for 17 hrs at 670°C. This phase is

Jan 1, 1949

By M. B. Bever, A. K. Jena

Equations for the heat effects of additions of mixtures of multicomponent phases to a solution have been derived in terms of the enthalpy interaction coefficients. By these equations and the measured composition dependence of the heat effects on addition of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions, values of the enthalpy in-teraction coefficients in tin-rich solutions at 541°K have been obtained. Analysis of these results in terms of the regular solution theory and the quasichemical theory suggests that near the melting point of the solvent association in the solution becomes important. SEVERAL recent papers have discussed the nature of dilute solutions on the basis of measured enthalpy interaction coefficients. l-3 These coefficients contribute to the understanding of the constitution of solutions and can be used for the evaluation of thermo-dynamic data of multicomponent systems. Their experimental determination, however, is laborious. This communication reports values of the enthalpy interaction coefficients of silver, cadmium, and gold in liquid tin-rich solutions obtained from the measured heat effects of additions of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions. These measurements were made in the course of the determination of the heats of formation of Ag-Cd solid solutions reported in a concurrent publication.4 THE HEAT EFFECT OF AN ADDITION TO A SOLVENT This analysis is concerned with the addition of a mixture of multicomponent phases from the temperature To to a solvent of known composition at temperature T. If Nmixture << Nsolvent, where N designates the gram-atoms involved, the heat effect per g-atom of mixture added can be expressed as (HT - HT )i = difference in heat contents of component element i in the mixture at T and To Q = heat effect on solution of the mixture at temperature T Also1 Q = S Xi [2] where ?Hi ,T,x = relative partial enthalpy per g-atom of i in solution at temperature T and composition of the solution x x = average of the atom fractions of the added material in solution before and after the addition The relative partial enthalpy ?Hi per g-atom of an element i in a dilute solution composed of a solvent 1 and the solutes j = 2, ... m is related to the interaction coefficients by the following equation5 ?Hi - ?Hi-?Hi,x1-1 + S n1ixj+ . . . +S...S...S nrixn2... Xnji...Xnmm+... [3] vhere Xj = atom fraction of solute j in the solution nri = the rth order enthalpy interaction coefficients, which can also be represented by the more general designation5 L(i)n2,n3...nm and nj may have any positive integral value or zero. For identification of various rth order interaction coefficients, nri is written as nn2i2,...nij,...nmm. Eqs. [1], [2], and [3] combine to give the following general equation for the heat effect on addition of a small quantity of a mixture to a large quantity of a dilute solution n = _?ga ?Ha,To + ? Xi(HT - HT o)i a. i + ?xi?Hi,X,i?1 + ??xnjixj + . . . + ???. . .?. . .?xinrix2n2. . . xnji. . . xnmm+ . . . [4] The first term on the right-hand side of this equation is the heat of decomposition at the addition temperature of the phases present in the mixture, the second term is the heat required to raise the temperature of

Jan 1, 1970