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By H. L. Gilbert, C. T. Anderson, W. J. Kroll

In a previous paper,' the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.% When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8 in. in diameter. The supply of direct current of high amperage for producing the desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flcxible tubing of the movable electrodc, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decsed to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 19oo"C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica accortling to the reaction: SiO² + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1949

By C. A. Siebert, D. J. Girardi

PRACTICALLY every metallurgical process in-volves, at some stage or another, the contact of a metal with a gas. Because of this, gas-metal re-actions are of great practical importance and have been subjected to numerous investigations. It has long been recognized that the presence of cuprous oxide in liquid copper has an important effect on its casting characteristics and .physical properties. This has led to the desirability of determining the quantitative relationships between cuprous oxide in the liquid copper and the usual gases present during processing. Such data are not only of practical importance but also of a theoretical interest in that they provide a means of applying the principles of physical chemistry to problems in applied metallurgy. The object of this investigation was to determine the quantitative relationship at equilibrium between the gases carbon monoxide and carbon dioxide and the cuprous oxide content of liquid copper. The reaction and its equilibrium constant may be expressed as follows: 2 Cu (liq) + CO2 (g) = Cu2O + CO (g) acu2o X aco/a2 cu X aco2 Here the underlined symbol Cu2O designates cuprous oxide dissolved in liquid copper and (a), the activity of the various constituents. The activities of carbon monoxide and carbon dioxide are assumed to be directly proportional to their re- spective partial pressures and the activities of cuprous oxide and copper are taken to be proportional to their respective mol fractions. The equilibrium constant may then be expressed as follows: K2 = Ncu2o X Pco [Ncu]2 X Pco2 where N = mol fraction The solubility of carbon monoxide and carbon dioxide in liquid copper is a rather controversial subject.'-' A review of the literature is given by 0. W. Ellis.' It appears that carbon monoxide and carbon dioxide are both only very slightly, if at all, soluble in liquid copper. Volskii and Slobodskoi5 determined the equilibrium between carbon monoxide, carbon dioxide, and liquid copper at 1100°C. Their results show a higher cuprous oxide content for a given CO/CO2 ratio than found in the present work. The system hydrogen, water vapor, and liquid copper was investigated by Allen and Hewitt8 over the temperature range of 1090" to 1350°C. Equilibrium values for the system carbon monoxide, carbon dioxide, and liquid copper calculated from these data agree reasonably well with the present work. Materials and Procedure The copper used was oxygen free, designated as OF and analyzed as 99.98 pct copper with no appreciable amount of any one impurity based upon spectrographic determinations. The carbon dioxide was cylinder gas averaging about 99.95 pct CO2 with air as the major impurity. The carbon monoxide was produced by passing carbon dioxide over heated charcoal. Alundum combustion boats were used as containers for the liquid copper. No appreciable reaction took place between the copper and the alumina. This was evident from the fact that the copper sample after a run did not ordinarily adhere to the bottom of the boat and that the

Jan 1, 1951

By J. van Lookeren

In the case of a reservoir where the oil underlies a large gas cap and overlies bottom water, production can be inzproved considerably if wells are perforated below the water-oil contact rather than opposite the oil-bearing section. The theoretical arguments for this improvement, which in some cases may be tenfold, are supported by experimental evidence. INTRODUCTION Reservoirs frequently consist of one sand body containing an oil layer underlying a thick, gas-bearing section and overlying bottom water (Fig. 1). Wells in such reservoirs are customarily opened up opposite the oil-bearing interval or, rather, opposite the lower part of this interval (Fig. 2). More often than not, it is inefficient or prohibited to blow off large quantities of gas with the oil. This im-psses a severe limitation on the drawdown, which results in low oil-production rates. Because of the small difference in specific gravity between oil and water, the latter will easily cone upwards, so that the production of water together with the oil is not prevented by this completion method. In such a situation wells should be opened deeper, in the originally water-bearing zone. The gas can be shut off by not perforating over the upper part of the interval (Fig. 3) or by a tubing hung close to the bottom of the interval (Fig. 4). Initially much water will be produced, but when steady-state conditions have been established (as depicted in Figs. 3 and 4) larger drawdowns are permissible than in a conventionally completed well, and correspondingly higher oil-production rates will result. Water cuts are only slightly higher because of the small effect of gravity on the water-oil flow distribution. CALCULATIONS The ratio of improvement has been estimated by means of approximate calculations. The completion depicted in Fig. 4 is the most convenient basis for these calculations. By postulating that vertical flow gradients can be disregarded, the Appendix shows that the well-known Dupuit formula can be obtained except for some complication due to the presence of two fluids rather than one. The Appendix makes the reasonable assumption that, for suitable boundary conditions, the oil layer occupies a constant fraction of the total fluid height throughout the reservoir. The oil- and water-production rates can thus be related to the liquid levels in the borehole as follows:

Jan 1, 1966

By P. M. Robinson, M. B. Bever

The heats oj formation at 273°K of the compounds CdTe, I)z2Te, InTe, In2Te3. In2Te5, SrzTe, and PbTe have been rleasrred in a liquid metal solutiotz caloritrete? 1.t1itlz bismuth as solvent. The?, are iterpretecl in yelation to tlze stability and bonding of the cott/pozltzds. Tile heats of fusion atzd the melting- points of tlze cotlzpounds InTe and Itzz,Te3 1lcti.e been measured in a cotrslant-temperature gradient calorimeter. The entropies of fusion are disc,ztssecl in YIIIS 01. the degree of order in the solid at the melting point. THE heats of formation of the tellurides of cadmium, indium, tin, and lead have been measured as a continuation of research on the thermodynamic properties of compounds of tellurim.' The tellurides of these metals were selected with a view to examining the relation between the heat of formation and the position of the metal in the periodic system. The elements cadmium, indium, and tin are in the same period and tin and lead are in the same group of the periodic system. The tellurides of indium are of special interest because four compounds, In2Te, InTe, In2Te3, and InzTe5, occur in this system. The available information on the heats of formation of the compounds investigated consists of values for CdTe, SnTe, and PbTe derived from electromotive-force measurements,J a value for CdTe obtained by tin solution alorimetr, and values for InTe and In2Te3 determined by combustion calorimetry.5 These values, however, refer to various temperatures ranging from 273' to 673°K and some of the reported error limits are large. Liquid metal solution calorime-try may be expected to yield more accurate values for the heats of formation than electromotive-force measurements or combustion calorimetry. The heats of fusion and the melting points of the compounds InTe and In,Te3 were determined in a constant-temperature gradient calorimeter. No published information appears to be available on the heat of fusion of these compounds. The results reported here give an indication of the degree of order in the solid compounds at the melting point. 1) MATERIALS AND EXPERIMENTAL PROCEDURE Materials. Samples of the compounds SnTe and PbTe were obtained from the Westinghouse Research Laboratories and samples of the compound InTe from Lincoln Laboratory, Massachusetts Institute of Tech- nology. Additional samples of the compounds InTe, SnTe, and PbTe and samples of CdTe, In2Te, In2Te3, and In,Tes were prepared from 99.995 pct Cd (Baker Chemical CO.), 99.999+ pct In (American Smelting and Refining Co.), 99.99 pct Sn (Baker Chemical Co.), 99.999+ pct Pb (Fisher Scientific Co.), and 99.999+ pct Te (American Smelting and Refining Co.). Stoichiometric amounts of the component elements were melted in sealed, evacuated Vycor tubes. The melts were held at approximately 100°C above the liquidus for about 16 hr and shaken repeatedly. The melts of the compounds In2Te and InzTe5, which form by peritectic reactions, were quenched into iced water. The melts of the other compounds, which have congruent melting points, were slowly cooled to room temperature. The samples were then annealed for 5 days at approximately 50°C below their respective solidus temperatures. Metallographic examination did not reveal any evidence of second phases or segregation. At least two batches of each compound were prepared. Samples from each batch were used in determining the heats of formation and, in the cases of InTe and In,Te3, the heats of fusion. The Heats of Formation. The heats of formation at 273°K of the compounds were measured by metal solution calorimetry with liquid bismuth at 623" as solvent. In this technique, the heat of formation is determined from the measured heat effects on dissolution of the compound and of a mechanical mixture of the component elements. The difference between these heat effects adjusted for changes in the composition of the bath gives the heat of formation at the temperature from which the samples are added to the bath (273°K). The experimental technique and method of calculation have been described in detail elsewhere.= It should be emphasized that the reported heats of formation depend on the thermodynamic data used in calculating the heat effects for the calibration additions. In the present investigation, the calorimeter was calibrated by adding pure bismuth at 273°K to the bismuth bath at 623°K. The reported heats of formation are based on a value of 4.96 kcal per g-atom for the difference in the heat contents of bismuth at 623" and 273". If a new value for this quantity becomes available, the reported results may be adjusted in direct proportion. The concentration of solute in the bath at the end of a calorimetric run did not exceed 1.7 at. pct and was usually less. In this range, the heat effect on dissolution of the solute was a linear function of the concentration of solute. In determining the heats of formation of the compounds in the system In-Te, a few runs were carried out in which two neighboring compounds such as InTe and In,Te3 and the corresponding mechanical mixtures of the components were added to the calorimeter. The

Jan 1, 1967

By Leonard Larson

Before direct or wet smelting of copper concentrate was adopted at the McGill smelter, in November 1932, actual furnace smelting tests had indicated the possibility of smelting between 400 and 500 dry tons of wet concentrate per furnace day. Under calcine smelting practice, solid charge up to 116; tons per furnace day had been smelted. It was realized that in order to smelt wet tonnage in equivalent amount per furnace day, a higher combustion rate and higher temperatures would be necessary within the furnace. The reverberatory furnace considered in the following history of wet-smelting developments is a unit rz7 ft. long and 28 ft. 8 in. wide, inside dimensions (Fig. I). This furnace was in operation through all the years from 1934 to date. During 1933, the first complete year of direct or wet smelting, the plant was on a curtailed copper-production basis and the available concentrate tonnage to be smelted was limited. The average coal-firing rate in the reverberatory for that year was 124 tons per furnace day. This rate was lower than the average for years immediately preceding under calcine smelting practice. With this coal-firing rate, an average of 391 tons of new metal-bearing material (N.M.B.M.) was smelted per furnace day. The following year, 1934, the coal-firing rate was increased to 139 tons and the smelting rate increased to 448 tons N.M.B.M. per fur- nace day. In succeeding years production required that either more tonnage be smelted in the one furnace or an additional furnace be placed in operation. With this situation confronting the smelting department, it was determined to continue the program of increasing the coal-firing rate and also to intensify the temperature in the smelting zone of the furnace. In order to accoinplish this, various improvements were made to aid combustion within the furnace. The burners were enlarged, increased primary air was supplied to the burners, and changes were made in the furnace to enlarge and streamline the outlet, thus increasing the furnace draft. The coal-firing rate was increased yearly until 1937 when the firing rate averaged 210 tons per furnace day. Thereafter the firing rate fluctuated according to character of charge and production requirements. In general, however, with the same character of charge the smelting rate increased in almost direct proportion to the increases in firing rate. Table I shows the average coal-firing rate, smelting rate, and other pertinent data for the direct-smelting years of 1933 to 1939 inclusive, the first fivc months of 1940 and May 1940. These figures show that the water evaporated in the waste-heat boilers was in almost direct proportion to the coal-firing rate. In making comparisons in the table, it should be borne in mind that the figures, except for May 1940, are yearly averages. Because of changes in character of charge or operating conditions, records for individual days or even months

Jan 1, 1944

By G. S. Scott, G. W. Jones

ECONOMIC waste caused by mine fires may become considerable,15 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters-such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control. necessarily must be based upon one or the other, or both, of these two principles. . The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion) ; and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. OXIDATION OF COAL Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored.6,16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By J. A. B. Forster

W. G. WOOLF*—The paper has a wealth of data that take careful, detailed study. As has been indicated the highlights can be only touched in the paper. The design and the arrangement of the rabble teeth as well as some of the other details of operation show a very careful study and a scientific approach to the problem which in most plants using hearth roasters are matters of trial and error with empirical conclusions and, perhaps too often, just arbitrary supervisory preferences which may be erroneous. Here the problem has been approached from a scientific angle which think well merits careful study. The ability to treat the tonnages they get through these furnaces think is made easier by reason of the high sulphide sulphur in the resulting calcines which the balance of the plant—the leaching and so on—can cope with. As indicated by Mr. Weldon in his dis- cussion earlier this morning, in most zinc plants an attempt is made to have as low a sulphide sulphur content in the roaster calcine as possible. But in the operation of the Risdon plants, they are able to cope with sulphide sulphur content up to 5 pct which is far beyond the amount of sulphide sulphur that can be handled elsewhere. I think the autogenous roasting is made easier because driving out the last percentages of sulphide sulphur brings on the necessity for extraneous heat, and that is further exemplified because even at Risdon the author shows the desirability of using some oil to better the operation, particularly for uniformity of roasting results and to obtain more regularity of furnace operation. A. A. CENTER*—Regarding the hard crusts in the beds of the furnace and autogenous roasting, the paper speaks of the former being due, at least to a considerable extent, to lead sulphide in the crusts. I wonder if the author has considered the hard crusts as being due in large part to zinc sulphate. While I was developing large zinc operations we ran into hard crusts which had to be dug up. I took several lumps which were so hard they showed the marks of the rabble teeth very plainly and kept them in my office for some weeks. A visitor came along one day, and as he was having similar troubles, I told him what we were doing about ours. I started to pick up one of these lumps and to my amazement the thing crumbled in my hands whereas originally it had been so hard it wore the rabbles down very rapidly in the furnace. I sent the sample to the laboratory and found that it analyzed very high in water-soluble zinc and sulphate-sulphur. The crumbling of the lumps was evidently due to the anhydrous zinc sulphate gradually taking on moisture from the air and forming crystalline zinc sulphate seven parts water. The increase in volume would, of course, result in disintegration of the lumps. As to getting a high tonnage in the autogenous roast, that is partly because of finishing at about 5 pct sulphide sulphur. It is a real job to get down to, say, ½ pct sulphide sulphur, which is what is usually desired, and still put through a good tonnage.

Jan 1, 1950

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By W. T. Lundy

THE forms in which sulphur is commonly found-native sulphur, sulphides of many metals and sulphates-are widely distributed throughout the world. The two first mentioned are the principal sources of sulphur. Substantial amounts of sulphur in some form are recovered from gases from industrial plants and from gases from smelters treating other minerals. In recent years, plants have been installed in the United States to recover sulphur in elemental form from sour gases."' The amount of sulphur so produced is small at the present time but undoubtedly will increase in the future. The recovery of sulphur from gases is not covered in this chapter, which is confined to: (1) native sulphur deposits of Texas and Louisiana; (2) those of Italy; (3) other scattered deposits of native sulphur; and (4) pyrites deposits found in many countries of the world.30 Sulphur, a nonmetallic element, occurs normally in well developed bipyramidal or tabular crystals of the orthorhombic system, as well as in stalactitic and earthy masses. The mineral has a distinctive yellow color, which may be dark and discolored by impurities; the streak is white; the luster is resinous; and the fracture is conchoidal to uneven. Sulphur is translucent to opaque; has a hardness of 1.5 to 2.5, a specific gravity of 2.05, and an atomic weight of 32.06.16 The molecular weight of the solid is expressed by the symbol SS and that of the liquid and vapor ranges from S2 to S8, depending on the temperature. Sulphur melts at a temperature between 2340 and 248°F, depending on its crystalline state, to a liquid of dark amber color, the boiling point of which is 832°F. The viscosity near the melting point is about that of water and increases to 50,000 times that of water at a temperature of 380°F, subsequently falling rapidly to a low figure at the boiling point. Crystallization changes slowly from rhombic to monoclinic above 205 °F and in cooling the transformation is reversed. The mineral is a very poor conductor of heat and electricity; it is insoluble in water and nearly all acids and is soluble in cold carbon bisulphide and carbon tetrachloride. It ignites in air at a temperature of 478°F, burning with a distinctive blue flame with evolution of sulphur dioxide.47

Jan 1, 1949

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By John E. Conley

THE slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5 ¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. USE OF WASTE SLATES FOR MAKING AGGREGATES The lightweight-aggregate industry has been discussed elsewhere4.5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. REQUIREMENTS FOR RAW MATERIALS As pointed out by Hughes,4 the light-weight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of any low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig. I illustrates the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By William Campbell

FiRst I must express my deep appreciation for the honor of being privileged to give the Howe Memorial Lecture this year and at the same time my feeling of inadequacy to do justice to the subject. The first Howe lecturer was most fittingly, Professor Sauveur, his contemporary and friend, and the subject was beta iron. Last year the second Howe lecture was delivered by Dr. Mathews, one of his most distinguished pupils, who spoke on austenite. This year, the Howe Professor of Metallurgy was chosen to deliver the third annual lecture, and the subject ought to be martensite. No one but Professor Sauveur could have brought to life what was considered by many to have been dead and buried, and he so persuasively and convincingly proved to us by his experiments the existence of something that the followers of that new cult "X-Ray and Crystal Structure " would have us believe is simply alpha iron. And Dr. Mathews from his wide practical experience was so easily able to convince us that austenite was not only the most wonderful of the iron-carbon series, but that it was the wonder alloy of the future. If I were to follow in the footsteps of my distinguished predecessors, I would talk to you about martensite. But when I had planned this lecture, I found that I was writing about Professor Howe and his work and his influence on the science of metals of today, and that martensite had become the secondary theme. And when finally I was obliged to choose a title, I remembered that it was in 1901 I came from Roberts-Austen with a letter of introduction to his very dear friend, Henry Marion Howe, at the Columbia School of Mines, to continue my work at the next bench to Dr. Mathews. Since then a quarter of a century has gone by, and during that time all branches of science seem to have been remade, so great has been our advancement in knowledge and discovery. And now that Metallography has finally established its place as an important branch of science, with its own textbooks and literature, I would like to review what seem to me to be the most important advances we have made in the last 25 years. To do this, I would start with Howe's "Iron, Steel and Other Alloys," and end with Jeffries and Archer's " Science of Metals." In the preface of the former, Professor Howe wrote: My warmest thanks are due to the friends who have aided me with their counsel and knowledge. In particular, let me thank most sincerely Prof. Margaret E. Maltby

Jan 1, 1926

By R. H. SWEETSERS

A Discussion of Mr. Hall's paper, read at the Washington Meeting, February, 1905. R. H. SWEETSER, Sault Ste. Marie, Ont. (communication to the Secretary*) :-The recent work of furnace No. 1 of The Algoma Steel Co., at Sault Ste. Marie, Ontario, using for fuel, first all charcoal, then a mixture of charcoal and coke, and finally all coke, upsets the estimates given by Mr. Hall in the last two paragraphs of his interesting paper. Furnace No. 1 was built for a charcoal-furnace, and it was run on charcoal fuel from March 6 until July 9, 1905; then, for a week, a mix¬ture of charcoal and coke was used, and, since then, coke alone has been the only fuel. It is to be regretted that at no time, during the run on charcoal, was there enough charcoal on hand and " in sight'" to warrant blowing the furnace as hard as it should have been blown. During April and May the supply of charcoal limited the amount of blast to about 8,000 cu. ft. of air per min.; in June, to about 8,900 cubic feet. For a few days in July about 10,000 cu. ft. were blown, and then the maximum daily output, 173 tons (2,240 1b.), was reached. At all times the quality of the charcoal was poor, having been made from wood cut from three to four years before. Doubtless this furnace could have produced .200 tons of iron per day, even with this quality of charcoal, provided the supply had been sufficient; and with good charcoal I see no reason why it could not make as much iron per day as it has made with coke. During the one week of using a mixture of charcoal and coke, the changes in quantity of blast and composition of the slag followed each other so closely that no single condition could last long on the furnace. The results were good, and the pig-iron was about the same in quality as that made during the

Jan 1, 1906

By A. J. Phillips, A. A. Smith, J. S. Smart

THE preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in properties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. PREPARATION OF HIGH-PURITY COPPER The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuS04-H2SO4 electrolyte using bagged anodes, low current .density (5 amp. per sq. ft.) and low temperature (25°C. max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe 2(S04)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then refiltered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2S04 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 434 by 43a by I-in anodes cast from high-quality electrolytic wire bar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars-which would result in fouling of the contacts and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By H. L. B. Gould, Jr. Wenny D. H.

TO date there has been but limited interest in alloys of 80 to 95 pct Co and Fe with or without other additions. In 1932, S. R. Williams' reported practically zero magnetostriction for the 90 pct Co-10 pct Fe alloy. This same composition was used for pole pieces to control the magnetic field in magnetrons operating at high temperatures.' In 1947, a 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn composition was investigated3 for use in ballast lamps because of its high temperature coefficient of resistance. Recently, as part of a survey of ductile and malleable magnetic alloys capable of being processed to thin gages for possible applications in memory devices, the high Co-Fe alloys have been re-examined to determine their fabricating and magnetic characteristics. Alloys from 80 up to 95 pct Co and Fe with and without additions such as vanadium were prepared. In general these all had excellent ductility and malleability. Wire was drawn to thin gages without difficulty and fine hard-drawn wires flattened to 2) The phenomenon may have potential in estimating the carbon content of molybdenum. A given solution-treating temperature and cooling rate could perhaps be calibrated so that the area fraction of surface covered by carbide could be interpreted in terms of carbon concentration. By segregating to the surface, a big "magnification" of the carbon content is obtained, which should make the method cheap, direct, and sensitive and, therefore, perhaps of interest to the molybdenum industry. This work was conducted at Battelle Memorial Institute. Financial support by the Aeronautical Systems Division, United States Air Force, under Contract No. AF 33(657)-7376, is gratefully acknowledged, and the writer is thankful for the experimental assistance of Miss Marjorie Cantin. ribbon without splitting. Similarly, strip was cold-rolled as much as 99.75 pct reduction to a 0.25 mil thickness without intermediate anneals. Samples of round and flat wire and foil, in the severely cold-worked and annealed states, were checked for magnetic characteristics. The alloys exhibited widely divergent magnetic characteristics depending on the processing and heat-treating procedures used in preparing the samples. Direct-current hysteresis loops showing the different magnetic characteristics of 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn alloys are shown in Figs. 1 to 8 inclusive, while Figs. 9 and 10 show the loops for an alloy of 82 pct Co, 11.75 pct Fe, 5.6 pct V, and 0.65 pct Mn. Figs. 1 and 2 show the high remanence and exceedingly square-loop characteristics of the hard-drawn wire and ribbon roll flattened therefrom. With the change in processing from roll flattening to flattening by drawing through flat diamond dies the resultant change in texture is accompanied by the drastic change in the shape of the loop as shown in Fig. 3. This skewed loop on annealing reverts to a more normal loop as shown in Fig. 8. The most unique loops are obtained with flat rolled strip. These are shown in Figs. 4 and 5. In the case of the hard-rolled material, Fig. 4, there is little change in induction until the magnetizing force reaches 50 oe. From 50 to 60 oe there is a sharp increase in induction to over 15,000 gauss, which for all practical purposes is saturation. The induction remains at a constant value while the magnetizing force decreases to 40 oe. At this point the

Jan 1, 1965

By Charles L. Guettel

The temperature coefficients of electrical resistance of 31 alloys in the nickel-rich corner of the Ni-Cr-Fe system were determined. The results indicate that a range of binary Ni-Cr alloys has lower temperature coefficients than a specific region of Ni-Cr-Fe alloys which has been reported and quoted by others as providing the lowest coefficients in the ternary system. DESIRABLE properties of resistivity and temperature coefficients of resistance have been the basis for the successful commercial application of various Ni-Cr and Ni-Cr-Fe alloys. In particular, low or negligible temperature coefficients of resistance are necessary for wire used in precision wire wound resistors and potentiometers involved in closely controlled electrical and electronic circuitry. Alloys most successfully applied to this purpose basically have not been ternary Ni-Cr-Fe alloys but rather heat-treated Ni-Cr alloys in the region of approximately 73 to 79 pct Ni and 20 pct Cr with significant additions of other elements such as aluminum, silicon, iron, copper, manganese, and cobalt. While the addition elements play a vital role in the nature and control of the temperature-resistance curve of any one of these alloys, the inherent relatively low temperature coefficient of the binary Ni-Cr base composition itself in the approximate region of 80 pct Ni and 20 pct Cr contributes fundamentally to the eventual negligible temperature coefficient obtained with the applied alloys. W. A. Dean 1 has reported mean temperature coefficients (20' to 100oC) of as-cast samples for the Ni-Cr-Fe system, the nickel corner of which is given in Fig. 1. Dean had to use as-cast samples because alloys from a considerable region of the system were unworkable. Dean refers to the work of Hunter and sebast2 who used annealed wire samples to show that, for chromium contents of 10 to 25 pct, the temperature coefficient increases as the iron content is increased at the expense of nickel. Although the data of Hunter and Sebast were limited in the nickel-rich areas to eight samples of 60 to 91 pct Ni with only four samples containing iron, the possibility that no Ni-Cr-Fe alloy has a lower temperature coefficient than certain binary Ni-Cr alloys should have been given serious consideration. However, Dean's work has been referred to by J. S. Marsh,3 who, quoting Dean, states that for the temperature coefficients "the smallest values-about 0.0001 per oC (100 ppm)—were found for alloys containing about 55 pct Ni and 20 pct Cr" (balance iron). A region such as that reported by Dean would be significant to those trying to develop alloys for the applications described. Therefore, a series of three-pound laboratory open-air induction melts of Ni-Cr and Ni-Cr-Fe alloys were melted, conventionally processed to 0.005 in. diam wire, and continuously strand annealed at 1900° F. The basic Ni-Cr compositions, with balances essentially iron other than usual minor impurities, and the corresponding temperature coefficients of resistance and resistivities are given in Table I. The resistivities are approximate and are not to be considered as a basis for relating them to their position of composition in the ternary system. The wire diameters were determined with a micrometer, and not by weight and density measurements which would be required for accurate resistivity values. However,

Jan 1, 1963

This paper "On Coal" was published in three issues of The Western Gleaner in 1814. Name of author is not given. This magazine was started by Cramer, Spear & Eichbaum, in Pittsburgh, Pa., in December 1813, and ran for about two years. Copies are very rare, and this one is made from an original in the Darlington Library, University of Pittsburgh. This is almost certainly the first general article on coal published west of the Allegheny Mountains, and one of the earliest in this country. ON COAL Its Natural History-Mining of Coal-Phenomena occasioned by Fire-damp-Method of Coking-Distillation of Tar from Pit-coal-Gas-light-Coal, a Manure I. NATURAL HISTORY OF COAL There are few productions of nature which present to the philosopher a wider field of investigation than pit-coal. A substance highly inflammable is found in the deep recesses of the earth, sometimes loaded with numerous superincumbent strata of hard rock, and extending frequently along with these strata through a vast expanse of territory. Though metals may be said to be inflammable substances, as they combine more or less rapidly with oxygen when placed under particular circumstances, yet the character of rapid combustion with disengagement of light and heat, seems to belong. principally to such substances as are derived either from the animal or vegetable kingdom. That this is probably the case with regard to coal we are further induced to believe, by the remarkable circumstance, that the chemical analysis of this natural production yields especially, though in various proportions, those materials which constitute essentially the vegetable. And if any thing was wanting to confirm, us in that opinion we might trace in a number of fossile substances the gradual transition of the vegetable into the state of mineral coal. This fact is so intimately connected with the natural history of coal, that we cannot think it superfluous to give it some farther development. Among the great number of principles which the chemist is capable of tracing in the vegetable kingdom, the presence of extract, resin and fibre seem to form the characteristical marks of plants.-If vegetable matter be boiled in water, and the water, after having been strained and filtered, be exposed for some time to the open air, a flocculent precipitate takes `place from every part of the liquor; which soon subsides to the bottom of the vessel containing it. This is the extract; altered, indeed, by exposure, and now no longer soluble in water, a change which is supposed to depend on the absorption of oxygen; and if, by any means the proportion of oxygen be increased, the extract gradually becomes of a darker color, blackens, and approaches to the state of charred wood.

Jan 1, 1942

By J. D. Edwards, C. S. Taylor, A. S. Russell

Solubilities and densities are reported for alumina hydrates in NaOH solutions under the conditions of the Bayer process employed to purify alumina for aluminum production. The equilibrium constants for reactions to form A102- accurately correlate the effects of NaOH concentration on the solubilities; the temperature coefficients of the equilibria lead to heats of solution of 7.34, 4.76, and 5.24 kcal for the a trihydrate, a monohydrate, and ß trihydrate, respectively. Moderate calcination does not change the solubility of the a trihydrate but increases that of the a monohydrate. At solution temperatures above 100°C, the trihydrates transform rapidly to a monohydrate. Hydro-thermally produced a monohydrate is the stable phase above 20°C. CORNERSTONE of the aluminum industry, the Bayer process for alumina production is based on the difference in solubility of hydrated alumina in NaOH solutions between 170" and 40°C. Solubilities and densities in this system were determined thirty years ago by M. Tosterudl under the direction of J. D. Edwards and C. S. Taylor. The solubility data, which still appear more concordant than those in the literature, are employed to sort out the complex equilibria in this system. The nomenclature for the alumina hydrates is that presented in The Aluminum Industry' and more recently summarized in Alumina Properties.3 a trihydrate is the purified phase analogous to gibbsite, a monohydrate is similarly akin to boehmite, and ß trihydrate is sometimes known as bayerite. Literature Goudriaan4 reviewed the early literature on alumina in NaOH solutions and presented data on the solubility at 30°C of several forms. The gel precipitated from aluminum sulphate or chloride with ammonia and dried at 130" to 140°C had the highest solubility but was unstable, its solubility being cut to one-tenth on standing in NaOH. The solubility of the gel was decreased one-third on calcination at 300" to 400°C, while that of the gel transformed in NaOH at room temperature to a crystalline trihydrate was unchanged on calcination. The preparation produced by slow hydrolysis of sodium aluminate solution with CO, in the air gave solubilities in rough agreement with later values for a trihydrate. The solubility of this form was increased slightly by the calcination. Fricke and Jucaitis5 extended the work to 30" and 60°C with a trihydrate. They also gave solubilities for ß trihydrate (bayerite b), although the residue belonging to the left branch of the solubility curve corresponded to a trihydrate. The residues at high NaOH concentrations were mono and trisodium aluminates, the latter being 3Na2O . AL2O3 • 6H2O. Solubilities of a trihydrate at 95°C and of a monohydrate at 150" and 200 °C come from the work of Magarchak.6 a trihydrate transformed to a monohydrate above 95°C. A few measurements on the solubility at 25°C of an alumina trihydrate prepared by slow hydrolysis of NaAIO, solutions were presented by Sprauer and pearce.? Their analyses showed the monosodium aluminate to have the composition Na2O.Al2O3-2.5H2O.

Jan 1, 1956

By Regis M. N. Pelloux, N. J. Grant

Five or six alloys each in the systems Ni-C.v, Ni-Mo, and NL-W, spaced to cover the single phase areas as well as a part of the adjacent two-phase field, were prepared as uacuum-melted alloys. Tensile tests at room temperature and stress rupture tests at 1200° and 1500°F we.ve run for time periods to give fracture in 0.1 to 500 hr. Observations mere made of solid-solution and second-phase strengthening or uleakening, coupled with studies of ductility and the role of structure on the noted behavior patterns. THE development of stable creep-resistant alloys while broad and systematic is also highly empirical. A number of simple rules have been suggestedL-" but these are based on scant data. Whereas rules for low-temperature alloy strengthening can be applied with some success in more simple systems, the extension to behavior at high temperatures (greater than about 0.4 of the absolute melting temperature) is very poorly understood and has encountered important exceptions and deviations in terms of atom size or valency effects. In particular, the occurrence of both solid-solution weakening4,5 and second-phase weakening2 at high temperatures is of interest. MATERIALS AND PROCEDURE Nickel was chosen as the base material because of its important role in current high-temperature alloy applications, because of its freedom from a phase transformation, and because of wide solubilities for many elements of interest. The selected alloys were single- and two-phase structures in the Ni-Cr,6 Ni-Mo,7 and Ni-w 8 systems. The alloys were vacuum melted and cast, utilizing high-purity raw materials, in the form of 15 lb ingots. They were readily forged into 1/2-in. bar stock (except the two highest chromium alloys). The alloy compositions are shown in Table I. Typical impurity values are: Carbon: Max 0.03 pct (except for 30 and 35 pct Cr alloys which had 0.07) Nitrogen: Max 0.005 pct (except for two of the Cr alloys which had 0.05) Sulfur: Max 0.004 pct Silicon: Max 0.05 pct Each alloy was solution treated (air quenched) to produce comparable grain size. The two-phase alloys were then overaged in an effort to produce a stable structure for testing at 1200° and 1500°F, The results are summarized in Table 11. Following the heat treatments outlined in Table 11, the bars were machined to a gage section of 1.25-in. long by 0.250-in. diam. In addition to room-temperature tensile tests, stress-rupture tests were run at 1200" and 1500°F for time periods from 0.1 to about 500 hr. RESULTS Room-Temperature Mechanical Properties—The ultimate tensile strength, total elongation, and reduction of area values for all the alloys are plotted vs atomic percent of the solute element in Fig. 1. It can be seen that for the same amount of solute element the ultimate tensile strength increases in the order chromium, molybdenum, tungsten. Elongation increases (reduction of area decreases) with increasing amounts of solute for all the solid solution alloys, the values ranging from 50 to 70 pct. The ultimate tensile strength values for the two-

Jan 1, 1961

By A. J. Chellew, Robert Condit

THE Company maintains a port agency at Antofagasta for dispatching copper and also for receiving from ocean vessels the vast variety of materials and supplies required at the plant. Copper shipments from the oxide plant refinery to Antofagasta amounted to 162,000 metric tons during 1951, while incoming freight totalled 175,000 metric tons. Electrolytic market copper in various shapes is currently loaded at the plant upon 20 or 30-ton cars of the meter-gage Antofagasta-Bolivia Railroad, to be transported a distance of 165 miles to the company's yard at Antofagasta. Here it is unloaded by cranes at the rate of about 175 tons per hr. Copper not scheduled for immediate shipment is stocked in tiers within the yard, but most of it is reloaded and sent to port works or a wharf serving lighters. Some of the vessels entering Antofagasta tie up at the port works, while others anchor inside the breakwater. In the latter case, all of the loading into the hatches is from 50-ton lighters towed to the vessel. When the vessel is at the dock, about half of the copper is loaded by port works cranes and the other half is loaded by ship's tackle from lighters. Fuel Oil Requirement Expands One of the innovations caused by the construction of the sulphide plant has been the necessity to provide facilities at Antofagasta for receiving and storing greater quantities of fuel oil than in recent years. From here it is loaded into tank cars for transportation to Chuquicamata. The older installation consisted of a 10-in. submarine pipe line, heating, and pumping facilities, a 67,500-bbl storage tank, and railroad loading rack, located at Antofagasta's northern limits. Two new tanks, of 80,000 and 30,000-bbl capacity respectively, have now been added and a second submarine pipe line will shortly be installed. Fuel oil requirements for the sulphide plant are estimated at 39,000 bbl per month, in addition to which 9000 bbl per month are required for the operation of the oxide plant. The company has a special lighter which is used by its diver for connecting the oil line with the oil tanker when disembarking oil, this lighter also being used for inspecting and overhauling buoys, as well as for recovery of bars of copper which are sometimes dropped into the bay when loading vessels during periods of rough weather. Transport of oil to Chuquicamata is by 76 tank cars of, 20-ton capacity and 20 of 30-ton capacity, all assigned to the company's fuel oil shipments excepting six for Diesel oil and one for gasoline. Incoming Freight Other freight received by the port agency has been averaging about 4800 metric tons per month of operating supplies for the oxide plant (renewals of equipment, spare parts, lubricating oils, and greases, etc.), some 1900 metric tons per month for the company stores, and about 6000 metric tons per month of materials and equipment for the construction of the sulphide plant. The greater part of these shipments (particularly the operating and construction supplies) originate from abroad, and must be handled through the Chilean Customs. Hence the company maintains a Customs storage warehouse (goods pending appraisal of Customs duties) in addition to its other storage facilities at Antofagasta. Not the least of the Port Agency's duties is to meet air and steamer passengers en route to Chuquicamata and to arrange for their trips up the hill. Landing in a strange country with a strange language, the first impressions of a new employee might otherwise be indeed confusing when facing Antofagasta's unique setting of brown barren hills.

Jan 1, 1952