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By Charles L. Mantell, P. P. Napolitano

High-purity tellurium oJ semiconductor grade may be prepared by a combination of electrowinning from tellurium oxide, electrorefining and controlled atmosphere melting, as detailed in the paper. SEMICONDUCTOR devices such as transistors and rectifiers depend upon extremely pure forms of silicon, germanium, and selenium. Although tellurium is chemically related to these elements, it has not been studied as a semiconductor because commercial forms are too impure. Highly purified tellurium would be an interesting starting point for a study of its solid-state characteristics. Tellurium shows a greater electrical conductivity in the direction of the helices or chains forming the crystals than at right angles to the chains, and thus is a semiconductor. Unlike selenium, the conductivity is only slightly increased by exposure to light. Impurities such as Ag, Cu, Au, Fe, Sn, As, Sb, Bi, Br, and I provide accepters and make extrinsic tellurium of the P type. So far, however, no elements have been found which, when introduced, would act as donors. Small amounts of tellurium dioxide enormously increase the thermoelectric power. Many extremely pure metals have been made by electrolytic refining or electrowinning procedures. Tellurium forms compounds in a number of valences, as indicated in Table I. The physical properties given in Table II do not show any unusual conditions which would interfere with the formation of elec- trodes, or the deposition of the metal on a cathode. Tellurium dioxide could be obtained in relatively high purities of 98 pct TeO2 or better at reasonable prices. Tellurium dioxide is soluble in caustic to form tellurites, which are conductive, ionizable, and from which tellurium metal may be deposited at a cathode. Preliminary solubility tests to saturation of tellurium dioxide in approximately 10 pct sodium hydroxide gave the results of Table III. The temperature range is a practical one for electroplating. Electrochemical test facilities were set up and these met the operating conditions of Table IV. For a determination of purity of deposits, there was available a Jarrell Ash Co. quantitative emission

Jan 1, 1964

OLIVIA'S recent revolution, by hindsight, seems to have been inevitable. The misery of the majority of the people, coupled with the economic crisis engendered by the refusal of the United States to meet Bolivian demands for a higher tin price, gave the National Revolutionary Movement party all the excuse it needed for overthrowing the government. Most of the mines in Bolivia are owned by three families. Precisely what it will mean to the United States is still a moot question. Argentina, with a mixture of Marxism, Fascism, and few twists created by the Perons, is in a position to grab off much of the tin we need. Because of the contingencies of geographical location, language and a natural simpatico, Argentina may be able to continue its efforts to oust the United States from its South American markets. Point Four aid was supposed to be given to Bolivia, but only for agriculture. Even this was entirely too slow. Mining, Bolivia's other major source of income was forgotten by the Washington planners. Primary aim of the new power will be to diminish its dependence on the world tin market. At a time when the free world is fighting a battle for control of metal, it stands a chance of losing an important source of supply. With the accent placed on agriculture and other industries, mining in Bolivia is certain to suffer. Argentina will be in a position to get the available supply of tin, make a strong ally in the world order of things, and add to its power play against the United States in South America. Ten labor groups have formed the Bolivian Central Workers Union. The first item on their list for immediate action is the nationalization of the mining and railroad industries. They also came out for agrarian revolution and diversification of industry. President Victor Paz Estenssoro has promised to appoint a committee for the investigation of nationalization of the mines. At least, this is indicative of a feeling for the need for caution.

Jan 1, 1952

By P. E. Demmler

Phosphorus combines with copper in various proportions, forming true alloys, some of which are of commercial importance. These materials find wide application as deoxidizers and as a means of introducing phosphorus into other alloys, as in phosphor-bronze. Phosphor-coppers containing 10 and 15 per cent. of phosphorus are the commercial grades that are most generally offered. Each has certain advantages when used in making other alloys. The 10 per cent, grade of phosphor-copper has an advantage over the 15 per cent. in that it has a much lower melting point and can be prepared by certain methods with a much lower loss in phosphorus. The 15 per cent. grade has the advantage of lower freight rates per unit of phosphorus and, by the method to be described, a uniform product can be prepared with practically no loss of phosphorus. Alloys of copper and phosphorus containing any desired percentage of phosphorus lower than 15 per cent. can be prepared by melting together the requisite amounts of copper and 15 per cent. phosphor-copper. Processes for making phosphor-copper may be divided into two classes as follows: (1) Those depending on the smelting of phosphate rock or superphosphate of calcium with copper or copper-bearing materials, and coal or other carbonaceous material; (2) those depending on the direct combination of metallic copper and elemental phosphorus. A number of formulas for preparing phosphor-copper according to the first method have been published. The Metal Industry' gives the following: Superphosphate of calcium, 60 lb.; granulated copper, 30 1b.; finely powdered coal, 10 1b. Similar formulas are given by Brannt2 and others, and detail variations are covered by patents, such as those of L. A. Jeffs3 and H. A. Webster.4 Among the objections to this method of producing phosphor-copper are the large amounts of raw material and resulting slag to be handled, and the difficulty of getting a satisfactory fusion. S. Skowronski5 found that at 1300' C. (2372' F.) it was impossible to get a good fusion

Jan 1, 1921

By W. T. Thom

In previous classifications of coal, it has been customary to regard moisture eliminated from coal samples between 20 and 100 C. as extraneous matter, rather than as a constituent part of the coal. It seems, however, that the physical character and use properties of the low-rank coals are directly related to the amount of such moisture present, and recent chemical work has shown' that such coals contain unstable groupings which decompose between 20 C. and temperatures somewhat above 100" C., with the splitting off of moisture. According to this view, the moisture eliminated from air-dried coal below boiling point is similar in all essential respects to moisture eliminated above 100" C., and is produced by analogous reactions; and inasmuch as the moisture given off above 100" C. has always been treated as a constituent of the volatile matter of coal, it would seem that consistent usage would include as a part of the volatile matter all moisture present as an essential component of the coal as it occurs in nature. As a matter of experience, it seems clear that the general physical and chemical characteristics of the low-rank coals are largely determined by or related to the moisture, whether chemically or physically combined, present in air-dried coal; it is also demonstrable by trial that the low-rank coals cannot be satisfactorily classified on a purely chemical basis by using the moisture free form of analysis. The low-rank coals of the western United States include numerous well-defined types, many of which were referred to in a classification proposed by Ashley,2 in which the physical and use properties of the coals were made the primary basis for their systematic grouping. When testing this classification by replotting analyses of these type coals according to the Seyler scheme of classification,3 a satisfactory parallelism between use properties and chemical constitution of the dry coal was found among

Jan 1, 1925

By K. M. Weigert

The position of the three-phase field between the alpha and the beta phases was established. The exact location differs from previous assumptions. The extremely high strength and hardness values were found near the phase boundaries of the ternary compositions. IN 1929, UenoL investigated vertical sections of the Ag-Cu-Zn diagram at constant silver and zinc values. From the evaluation of cooling curves and microscopic studies, he concluded that there was no evidence of a three-phase field in the solid state between the a and ,8 fields. The failure to find evidence for this field was due to the fact that it exists only in a very narrow range of compositions and requires special methods of heat treatment to establish phase equilibrium. In a later publication on the same subject Keinert2 rearranged Ueno's diagrams to conform with the basic phase rules. The existence of a three-phase field was postulated in the solid state between the a phases and the homogeneous ,9 phase between the Cu-Zn and the Ag-Zn binary border systems. The approximate location was based on a few microscopic observations of the structure and it was pointed out that the exact position could be determined only by a larger number of experiments. In the twenty years following these investigations alloys of Ag-Cu-Zn have become of general interest due to various technical applications, principally for brazing. In the course of an overall investigation of the physical properties of ternary Ag-Cu-Zn alloys the author found extremely high values of hardness and strength in alloys of compositions between the a and the yS fields. The exact location of the intermediate phase fields was established by the evaluation of more than a hundred cooling curves and microscopic mountings. Experimental Procedures Preparation of Test Samples: At the beginning of the investigation samples were chillcast into Vi in. diameter iron molds to determine hardness, strength, and the mechanism of primary crystallization. These

Jan 1, 1955

By Bernard York, John J. Reed

W. 0. Philbrook (Carnegie Institute of Technology, Phila.)—Mr. DeVaney's paper is a valuable addition to the growing technology of the magnetic roasting of lean iron ores. His furnace is ingeniously designed to permit close control of the process and to achieve high thermal efficiency by counter-current heat exchange and the withdrawal of both solid and gaseous products at relatively low temperatures. The principle of using a lean reducing gas to avoid over-reduction of the ore even at high operating temperatures (for rapid reaction rate) is thoroughly sound. The gas analyses and flow rates reported, however, are internally incon- sistent and render suspect any details of a heat balance based upon them. While it is entirely proper to consider the entrant gas as a reagent and to account only for the heat evolved by consuming a portion of the gas, many operators are accustomed to a heat balance using the total calorific value of the reagent supplied; and comparison of heat balances made with different bases of calculation can be quite misleading. Since Mr. DeVaney's paper is likely to be cited frequently in future discussions of magnetic roasting processes, it seems worth while to point out the internal discrepancies and to give alternate values of heat requirements for different bases of calculation.

Jan 1, 1954

By Bruce A. Kennedy

The 1960's were an apparent turning point in the technological and social attitudes and awareness of the mining industry. From the late 19th century through to the early 20th century, one has always been presented with the picture of the rough and ready leaders of the mining industry who screamed for production and damned anything that got in the way of it. This attitude led to a certain alienation of the mining industry in the eyes of the general public. They saw an industry which was archaic in many of its practices and often heartless in its attitudes towards mankind. However, a gradual change spread through the industry and cracks began to appear in the hard facades of the mining companies. Resistance to change had almost become a standard operating procedure for many and consequently changes in technology had been slow in coming. The late 1950's and the 1960's saw a new awareness come into existence. As the mining company managements changed, there developed a realization that considerable efforts had to be made to bring the technology and social standing of the industry out of the dark ages and into the modern world. New advances were made in both metallurgical and mining technology. The 20th century technology of computers was accepted and became a standard tool of the industry.

Jan 1, 1971

By W. Hume-Rothery

IN recent interesting papers,1,2 Bardos et al. have described ternary Laves phases of the type A2(BsSi) and A4(B5Si3) where A = titanium vanadium, niobium, and so forth, and B = manganese, iron, cobalt, or nickel; other more complex formulae have also been established. In these phases, silicon plays the part of the smaller B atom of a Laves phase AB2, and the interatomic distances show that the effec- tive silicon radii lie between 1.16 and 1.21Å, and are thus very much smaller than the metallic radius of silicon for CN = 12. It does not seem to have been pointed out that these small atomic radii are almost the sape as the normal covalent radius of silicon (1.174Å). If, therefore, silicon acts as an acceptor of electrons as suggested by Bardos et al.,1 it appears to do so, not by the building up of a negatively charged silicon ion which would be large, but by the formation of what are very nearly or may be actually normal covalent bonds. Since a covalent bond contains two electrons, its formation would reduce the number of electrons available for bonding in other parts of the structure, and in this way the effect of silicon in stabilizing the o phase at high electron concentrations might be understood.

Jan 1, 1965

By D. H. Newland

On the bulk basis New York's contribution to the production of oil is small, representing, as it does, a bare half of one per cent of the annual total for the United States. Yet it has more importance than is implied by such a statement. Petroleum includes a variety of organic compounds, some more and some less valuable. It would be a fairer estimate of the situation to say that New York in recent years has produced around 10 to 12 per cent on the average of all Pennsylvania grade oil, the supply of which is strictly limited and the demand steady even in times of overproduction of other grades. One may not infer from this that New York and other Appalachian states enjoy an independent position in the market with a price structure uninfluenced by that of the Mid-Continent, Gulf or California fields. On the other hand, the recent market demoralization in the South and West brought about by uncontrolled production caused prices to drop to a point where the life of the local industry was seriously threatened. The current cost of producing oil in New York under the methods of water-flooding, by which most of the output is now obtained, has been estimated by competent authority at not less than $2.50 a barrel. The

Jan 1, 1934

By R. V. Lundquist

R. T. Hukki (Finland Institute of Technology, Helsinki, Finland)—Two schools of thought are developing concerning the order of the rate of flotation. The paper by Morris is intended to show experimental evidence in favor of the first order rate. Arbiter, on the other hand, has presented an earlier paper" to demonstrate the validity of the second order rate equation. Unfortunately his method of plotting is open to criticism, as pointed out by Morris." A more sensitive method of plotting has been described by the writer,= whereby the data presented by Arbiter demonstrate the superiority of the second order plot. The general rate equation may be written in the following forms for the integrated first and second order equations: (A) t =------In—-------- (first order) [4] 1 1 (B) — = — kc, + KC°²— (second order) [5] t R As a first approximation the value of C, may be taken as a unity, 100 pct or 1. Whether or not this is the case in all tests performed by Morris is impossible to judge, owing to the fact that the flotation times are extremely short, e.g. 150 sec in tests A. It would, indeed, be very interesting to know what the total recovery R would be after 1 hr of flotation, for example, instead of after 150 sec. Certainly there are circumstances when C, approaches unity within a very small

Jan 1, 1954

By Walter Gaby

L. C. GRATON, Cambridge, Mass.-May I ask, in connection with one point in the summary, to what extent the author regards actinolite equivalent to tourmaline as an index of high-temperature and presumably magmatic conditions of deposition of the accompanying sulphides? W. E. GARY.-I merely advanced the idea that the mineral actinolite might have some such significance. In the copper deposit at Braden in South America, the ore occurs in an andesite breccia which is cemented by a matrix of sulphides, quartz, and tourmaline. Tourmaline is a high-temperature mineral, and when we find it associated with ores, these are regarded as having come from a volcanic or deep-seated source, hence a primary hypogenetic deposit. Thus we can count on greater continuation of the ore with depth than in some other kinds of deposit, and I thought that the actinolite, being also a high-temperature mineral, might have some such bearing in the case of Mount Morgan. I did not advance this idea as a final conclusion from a study of such phenomena, but thought that it might bear some discussion in view of the fact of the peculiar occurrence of this mineral in a notable orebody. It also occurs with the copper ores at Ducktown, Tenn., and in both cases may only be due to general regional metamorphism.

Jan 12, 1916

TWO very interesting sessions on mine ventilation were held on Monday. George S. Rice, chairman of the Mine Ventilation Committee, presided at the morn-ing session. Formal reports from two subcommittees were presented, as well as two technical papers. Daniel Harrington, for the subcommittee on metal mining, gave a most interesting report, devoting most of it to a review of the literature that had appeared during the past year, to the cooling of mine air, and to a discussion of mine fires. In the absence of Dr. R. R. Sayers, chairman of the Physiological subcommittee, Mr. Harrington gave a resume of that report. The main points covered were in connection with silicosis but some attention was also paid to the associated prob-lems of air cooling and humidity. The paper by Prof. W. S. Weeks on the "Air-Current Regulator" was briefed by Prof. A. C. Callen. Pro-fessor Weeks brought out the fact that the common application of Murgue's equivalent-orifice formula to regulator problems was incorrect, inasmuch as the dis-charge from the regulator was not released into the open air but into a slow-moving current beyond the regulator. He applied the shock-loss theory of Bordoni to the problem and worked out a formula for solving regulator problems, giving coefficients of contraction he had determined experimentally.

Jan 3, 1928

J. J. RUTLEDGE,* McAlester, Okla. (written discussiont).-Research work has often a more immediate and practical application to the in-dustries than even the investigators themselves realize, but coal mining has not attracted the investigator, except in so far as the mine-accident prevention work and fuel investigations are concerned. In future, the coal geologist will study the subsurface geology of the various coal seams as the petroleum geologist now studies the oil sands, and from the results of these studies the coal operator will be able to locate his shafts to the best possible advantage and to avoid faults that would interfere with underground work. There would have been many thousands of dollars saved, and perhaps some reputations, if a good stratigrapher. had been called into consultation in the southern part of Somerset County, Pa., where a local seam of coal, quite thick, was mistaken for the Pittsburgh seam, which, if ever present at that point, had long since been eroded. Why will the Quemanhoming coal carry more sulfur without injuring the grate bars than George's Creek Big Vein? Only the investigator can answer and yet the fact that the above is true means a greater price for the thinner coal. The owner of the land in Oklahoma receives one-fourth of the cotton crop produced by the tenant who farms his land and one-third of the

Jan 11, 1919

By T. V. Philip, R. E. Lenhart

C. G. Dunn(General Electric Research Laboratory)— It is well recognized that understanding of the formation of the cube-on-edge texture in annealed commercial cold-rolled Si-Fe strip is important industrially as well as scientifically. I would like to make a few remarks on this subject, discuss some points in the present paper, and list two remaining problems that appear to be particularly outstanding. Attention should be drawn to the paper by P. K. Koh,23 which also considers the kinetics of secondary recrystallization in 3 pet Si-Fe, produced commercially by the Allegheny Ludlum Steel Corp. Koh covered a much larger temperature range than do either the present authors or P. N. Richards, whose work is mentioned in a footnote. Koh found an induction period (of short duration) even for isothermal anneals at 1260oC (2300°F). Koh and Dunn24 also found a change in texture during the 1260oC anneal for the same material. On the other hand, the material in coil D, according to Philip and Lenhart, underwent no sec-condary recrystallization, only continuous grain growth. The grade classifications of the four coils studied would suggest, however, that all four materials had developed the cube-on-edge or (110) [001] texture, but to varying degrees. Since no data on this are given and since watt loss depends

Jan 1, 1962

By M. J. Salkind

In discussing the possible contribution of plastic deformation to neck growth during sintering, Wilson and Shewmon State that Lenel, Ansell, Salkind, and Early34, 35 concluded that dislocation flow is the rate-controlling process in sintering under zero external load. The experiments cited34, 35 were done with applied external loads, and the conclusions were that the same kinetics could be controlling sintering due to the force of gravity with no additional applied load. The effect of gravity on sintering behavior was previously cited.34, 31 In addition, Wilson and Shewmon argue that the conclusions of Refs. 34 and 35 are doubtful because the strain rate is proportional to stress for plastic flow. This assumption is true only for certain kinds of plastic flow such as Nabarro-Herring Microcree38 As Early, Lenel, and Ansell point out3' plastic flow, based upon dislocation movement, can exhibit strain rates which exhibit a power law relationship to the applied stress.39, 40 Wilson and Shewmon also doubt the results of Refs. 34 and 35 because the stresses in the necks are too small for x/a > 0.1. This is true, and the experiments described in Refs. 34 and 35 were done for small values of %/a. The conclusion was that plastic flow by dislocation movement was important during the early stages of sintering when x/a is small.

Jan 1, 1968

By Bjorn Bolviken

Bjorn Bolviken (Geochemist, Geological Survey of Norway, Trondheim, Norway)-Under the heading "Recognition of Anomalies," the author states, "If the frequency distribution is actually log-normal, the probability of these high values being part of the background population is small (less than 0.023 and 0.0013 for 2 and 3 standard deviation, respectively)." The figures quoted seem to be the probabilities of these high values being the mean rather than part of the background population unless "background" is defined as one single concentration. If the background is considered to be a statistical distribution of concentrations,50 (which is probably the case here since the author uses the term "background population"), the probability of any observed value being part of the background may be estimated through a calculation of the number of observed values that are in excess of (or below) the number expected to belong to the background. Apparently, some confusion exists in the literature regarding this point. Many authors accept the concept of background as being a statistical distribution, but do not seem to recognize the consequences of this concept. One of these consequences would be that the background of a chemical element should comprise any concentration between zero and a theoretical maximum, which is governed by the chemistry and mineralogy of the material

Jan 1, 1974

By J. J. Kanter

A. I. Blank.*-—Mr. Kanter has spoken of failures from causes other than creep itself in metals that are subjected to creep stresses. Would it be possible for the author to enlarge on this very important matter of "cataclysmic types of failures? " J. J. Kanter.—Of course, it is always a delicate matter to discuss specific failures. I would prefer to keep the present discussion on fundamentals and principles. H. L. Burghof.*—Mr. Kanter, I should like to ask what you consider the responsibility of the designer in avoiding stress concentrations that would lead to these types of failures? J. J. Kanter.—lt was my feeling in looking over the papers of this symposium that they were significantly lacking in consideration of what happens to the metals when strained under conditions that lead to rupture. Often creep tests are run that produce only a fractional percentage of the deformation, in several thousand hours. That kind of information gives the designer no assurance whatever that cracks will not result in his structure at points where stress concentrations, and therefore deformation concentrations, exist. I think anyone in this day and age who presents a paper on creep should incorporate with those studies a thorough investigation of creep rupture if it is expected to make an impression upon the design engineer.

Jan 1, 1945

By Colin Rae

THE absence of paraffin and other oil hydrocarbons in the soil, although they are concentrated in extensive deposits in some localities, the common distribution of plant remains through many formations that .are not productive for oil, and many other factors, seem to indicate the existence of an intermediate organic compound between the complex plant compounds and the petroleum hydrocarbons; and much evidence points to the humus acids or associated organic compounds, which are probably collected by surface waters and concentrated in certain areas by means of precipitation by electrolytes, which would be contained in sea water or possibly in various inland seas or lakes. PRESENT-DAY EVIDENCE There are many present-day evidences of the association of petroleum with humus acids. Binney, in 1912, made observations without explanations on the peat mosses of Down Holland, England, where he found petroleum being formed by decomposition, in the presence of an infiltration of sea water. The analysis of a typical peat will show its relationship to the humus acids under consideration. SAMPLE 'No. 1, SAMPLE NO. 2, PER CENT. PER CENT. Water : 20.0 29.5 Ash 3.0 3.05 Fiber 47.0 54.95 Humus acids 30:0 12.50 J. D. Haseman and others have noted the association of asphalt and hydrocarbons with the swampy, boggy areas, particularly adjacent to the sea.

Jan 2, 1922

FRANK N. SPELLER,? Pittsburgh,. Pa.-Mr. -Hayward's paper again draws attention to the fact that copper in steel is not the enemy that a good many of us it one time thought it was. He shows clearly that steel with over 0.75 per cent. of copper is as dependable, under the :conditions which he describes, as the same steel without copper. I might add that you-can weld copper-steel- satisfactorily up to that point; in fact, we have succeeded in welding pipe by the lap weld process up to 1 per cent. copper. Notwithstanding the date that have been presented on the effects of copper on the physical properties and corrosion of steel, a maximum copper limitation is still found in many specifications. In some cases the limit is extremely low, such as below 0.05 .or 0.03: per cent., or thereabout. That is a relic of days gone by, and I think the practice should be discouraged. E. F. CONE, New York; N. Y.-Not so many years ago steel-casting makers were very particular as to the amount of copper that existed in the pig iron that they used. They would not use copper-bearing pig iron unless mixed with non-copper iron. I do not know what the practice now is in the particular foundry where I was metallurgist at one time,

Jan 4, 1918

By P. P. Gregory

NATURAL petroleum gas occurring in the oil-bearing reservoirs is found to exist either as free gas associated with the oil and/or in solution in the oil. In some virgin fields practically no free gas is encountered under the reservoir conditions of pressure and temperature, although in other fields a considerable section of the ``pay" horizon is occupied by free gas. In other words, a given oil field may or may not have a gas cap before the exploitation takes place. However, when the reservoir pressure is reduced to a point below the critical saturation pressure by withdrawals of fluids from the producing formation, the gas dissolved in the oil inevitably begins to come out of solution and becomes free gas. Under the con-trolled methods of production and drilling, a portion of this gas is pro-duced with the oil to the surface and a portion of it remains within the reservoir to accumulate at higher structural levels toward which it migrates by virtue of its low specific gravity. The rate of growth of a gas cap in a-given structure depends primarily upon the rate of decline in the reservoir pressure. If the rate of pressure decline is rapid, the gas cap likewise will grog rapidly. On the other hand, shrinkage in the gas-cap area was noted in some fields in which reservoir pressures were increasing.

Jan 1, 1938