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By W. J. Moore, E. M. Swiggard, H. Shenker

Beryllium is the most soluble of the double-acceptor impurities in germanium; the solubility is at least 1 x 10 19 atoms cm3. Photoconductive, optical, and electrical measurements were made on a set of Ge:Be samples grown without other intentionally added imp~ivities. The excited-states spectrum of beryllium in germanium was determined both in zero field and in magnetic fields up to 30 kc. It was found that the absorption 0-f lines in the vicinity of the G line increased markedly with increasing magnetic field. The ioniza-tion energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mez: using the excited-states spectrum. An infrared detector using a Ge:Be element was found to have a normalized detectivity D* (50 p, 1000 cps, 1 cps) of 9 X ldO cm-~ps"~-w-'. The Ge:Be sambles exhibited low-field breakdown and inibzirity band conduction effects at low temperatures. WHILE the properties of most dopants in germanium have been thoroughly investigated, the properties of beryllium in germanium have had relatively little attention. Much of the work that has been done' has been concerned with the properties of singly ionized beryllium in germanium. The purpose of the present work was to determine the photoconductive and electrical properties of beryllium-doped germanium (Ge:~e) with a small concentration of other electrically active impurities. Ge:Be is of special interest since beryllium is the most soluble of the known double-acceptor impurities in germanium. MATERIALS PREPARATION A set of &:Be crystals with beryllium concentrations between 5 x 1013 and 1x 10'' cmm3 and without other intentionally added impurities was grown in a hydrogen atmosphere by the horizontal zone-refining techniques described by Swiggard and Shenker.2 The segregation coefficient of beryllium in germanium was found to be about 0.07 and its maximum solubility was found to be greater than 1 x 10'' atoms cm-3 which is in agreement with previous results.' Most of the crystals were found to have a small net concentration of shallow acceptors; for example, a crystal having a beryllium concentration of 1.1 X 1016 cm-3 was found to have a net concentration of shallow acceptors of less than 1.5 X 1013 cm-3. Ingots designed to have a beryllium concentration of 1 x 1017 cm-3 or less exhibited a loss of electrically active beryllium. That is, the beryllium concentration was lower than expected and the decrease of the beryllium concentration along the length of the ingot was much larger than expected. It is hypothesized that this effect is due to the oxidation of the beryllium by the residual oxygen in the system. This effect is similar to but not as severe as the effect observed with boron in germani~m.3, 4 OPTICAL ABSORPTION SPECTRUM The excited-states spectrum of neutral beryllium atoms in germanium was studied by measuring the infrared optical absorption spectrum. A typical spectrum is shown in Fig. 1; the labeling of the absorption lines follows that of Fisher and Fan.* The spacings between the observed lines and the D line are nearly equal to the corresponding spacings for the other ac -ceptors in germanium.5-7 By the use of the theoretical result67' that the neutral impurity ionization energy is 2.53 mev larger than the energy of the D line, the ionization energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mev at 4.2"K. This method yields a more precise value of the impurity ionization energy than the usual Hall effect method.' The absorption spectrum of Ge:Be was also measured as a function of magnetic field using a magnetic field parallel to the incident radiation and using unpolarized radiation. A typical spectrum taken at 30 kG is shown in Fig. 2. An unexpected observation is that the absorption of the lines in the vicinity of the G line (there is a strong possibility that some of these lines may be associated with lines other than the G line) increases with magnetic field. RESISTIVITY AND HALL DATA Measurements of Hall voltage vs temperature were made on several of the samples. The thermal activa-

Jan 1, 1968

By J. H. Bechtold

Tensile properties of annealed molybdenum were investigated from 1000" to—200°C. In the vicinity of room temperature a well-defined transition in tensile properties occurs. Reduction in area decreases from over 80 pct to 0 pct and, simultaneously, the yield strength increases about 60,000 psi. MOLYBDENUM, tungsten, iron, and many other metals and alloys with the body-centered cubic and hexagonal close-packed crystal structures change from ductile to brittle behavior over some relatively narrow temperature range. The temperature at which this transition in ductility occurs depends on chemical composition, microstructure, and method of testing. When fine grained, completely recrystallized molybdenum of commercial purity is tested in uniaxial tension at a slow strain rate, the transition occurs at slightly below room temperature.' Iron2 and tungsten3 tested under similar conditions become brittle at temperatures close to the boiling point of nitrogen, — 195°C and at about 200°C, respectively. A sharp change in ductility is uncommon in metals with the face-centered cubic crystal structure, however, a relatively sharp transi- tion in notched bar impact properties has been observed below room temperature in a face-centered cubic copper-antimony alloy.4 A transition from ductile to brittle behavior is usually explained by the concepts originally developed by Ludwik,5 and discussed and elaborated on by others including Orowan,6 Hollomon and Jaffe,7 and Gensamer8 In brief, there are two aspects to strength, first the resistance to flow and second the resistance to fracture. Both are functions of temperature, strain, strain rate, stress system, composition, and microstructure. With decreased test temperature the flow stress required to initiate plastic deformation increases more rapidly than the fracture strength and brittle fracture occurs at that temperature where the yield strength equals or exceeds a brittle fracture strength. This investigation was conducted to determine the effects of temperature, strain, and rate of straining on the flow and fracture strengths of molybdenum above, through, and below the ductile-to-brittle transition. Other variables were held constant during testing. This information is believed to show

Jan 1, 1954

By Raymond C. Johnson

GASIFICATION is important to the anthracite industry, as it is to the entire solid-fuel industry and to the nation. However, to the anthracite industry it may have particular significance in that it would increase the market value of many millions of tons of a by-product fuel, which the industry now has in storage and is currently producing, in addition to increasing the potential market for all its products. The by-product fuel is of usable quality but the ash content is higher than it can be in other products and therefore it must be converted or used at the point of production. Gasification is one method by which the product may be given increased value. The inherent characteristics of anthracite make it well suited for producing a fuel or synthesis gas. It is the most concentrated form of natural commercial carbon, noncaking and noncoking; it does not produce smoke, tar, or soot and has a low sulphur content; and the volatile matter, which ranges between 2 and 8 pct, is 80 to 85 pct hydrogen with small amounts of methane, carbon dioxide, carbon monoxide, and nitrogen. The ash fuses at high temperatures, which allows it to be burned at high rates without slagging. However, with the addition of small amounts of dolomite, the ash will form a slag, or glass, which is very fluid. Anthracite has long been used in the manufacture of city gas and it is extensively used in various parts of the country to make water gas to be converted to hydrogen. Buckwheat and rice anthracite are used in Galusha producers to make producer gas. Excellent synthesis gas has been made in a Galusha producer with rice and barley anthracite with oxygen in tests at the Consolidated Mining and Smelting Co., Trail, British Columbia. In these tests, anthracite was shown to have advantages over competitive fuels, in that the gas had a higher hydrogen content and could be cleaned with less difficulty. The anthracite seams are steeply pitching and in mining the parting strata and some of the roof and bottom materials are taken with the coal. In preparation, these materials are separated by gravity from the commercial product and stored in refuse banks. This refuse contains a mixture of rock, slate, or shale, and high-ash anthracite with bone coal, which is low-ash coal that is interspersed with thin bands of shale. The bone coal contains between 25 and 50 pct ash with an average ash content of approximately 30 pct, with a

Jan 1, 1953

By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8,9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation. was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, ½ in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6,9 The measure of internal friction adopted here, 1/Q, is (1/p) X the logarithmic decrement, a measure used by some writers, and is also (1/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the funda¬mental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. 1, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of l00 during the next 100° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e~H/RT [I]

Jan 1, 1942

By Franklin H. Wilson

COPPER base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pct silicon shows an attractive combination of high strength with excellent machinability. Since there is no evidence in the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. ALLOYS STUDIED For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An [ ] excess of 0.05 pct silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 ¼ by 1 ¼ in. were cast using Durville type casting equipment. Analyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pct of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1948

By Scott Turner

HOSTS of friends will rejoice that T. A. Rickard has been given honorary membership in the Institute. It might well have been done long ago, since, when one reviews distinguished services rendered by individuals to our organization and our profession, it is at once apparent that his name ranks high and that he has merited this distinction for more than three decades. Our by-laws restrict this list to twenty names; "T.A." becomes the sixteenth living member. Young engineers should particularly be pleased; Mr. Rickard has had a career rich in human interest, and full of useful suggestions to the younger men; he has given them good advice and set them a notable example; he, more than anyone else, has shown them how technical writing can be clear and concise; he has inspired youngsters to do their best; he has been their friend. No one has more first-hand knowledge of these facts than the writer of this appreciation:

Jan 1, 1935

By Bauer, Alan

In considering blasting it is necessary to consider the drilling and explosives since one is generally concerned with the total cost of muck of a certain size in the pit or through the crusher. To get a current idea of the drilling situation in open pit mines plotted in Fig. 1 are the drilling costs per ton of material vs. hole diameter for rotary drill holes in large limestone, iron ore and taconite operations. The exception is the 2-in. diam hole which was drilled with a percussion drill in limestone.

Jan 1, 1968

By E. C. Weichel

THERE have been many attempts at permanent roof support in anthracite mines, in some cases brick arches, in others concrete, and also combinations of brick or concrete walls with steel beams. These supposedly permanent roof supports have frequently failed when heavy pressure is brought to bear upon the structure, because they are so rigid that failure occurs because the structure is unable to adjust itself to the increased load. Roof pressure exerts a tremendous weight, and it is at times difficult to find any means of support which is strong enough to bear the entire pressure, unless this supporting structure has in itself the element of some flexibility which will enable the structure to hold the moving mass until it "arches" itself. If the supporting medium has flexibility enough so that it can adjust itself to the heavy initial loads, and so give the overlying material an opportunity to form a self-supporting arch, then such a roof support will be more useful than any rigid roof support. There has recently been introduced into the anthracite region a new form of gangway lining that is flexible enough to slightly adjust itself under heavy pressures, and so give the loosened material which is being supported a chance to form into an "arched" mass. This lining, manufactured under patents granted to Hans Schaefer of Essen, Germany, was introduced in the United States in the summer of 1928, at which time the Amercan licensee, Richard Howells of

Jan 1, 1930

By Sheldon P. Wirnpfen

AN extensive study of German underground manufacturing experience is being undertaken by the Air Materiel Command. Headquarters officials consider completely underground facilities one of the most effective means of protecting aircraft production against air attacks of the strength and type employed in World War II. Advantages accruing to underground manufacturing installations other than protection are, perhaps, a smaller maintenance problem and the possibility of using gravity flow on some production lines. Offsetting these advantages are the high cost of construction, problems of ventilation, and poor acoustics. Excavation costs might well be less than the cost of enclosing the same area on the surface, as new and better methods of rock drilling and transportation are developed. Certainly the amount of building materials used would be far less than in constructing a surface plant of the same dimensions. A fewer number of skilled workers would be required to perform the labor of excavation. Underground construction would

Jan 1, 1947

The question, Who won the war?, has been the text for innumerable newspaper, and magazine articles, the answers running from "bread and butter" to "poison gas," in a material sense, and from the "Y. M. C. A." to the "boys in the front lines," humanly speaking. Personally, I think the margin by which success was secured was so narrow that none of the complex, interdependent factors could have been .spared, and that, as Admiral Sampson said after the battle of Santiago: "There is glory, enough for all." But if any one human factor can be said to have been absolutely indispensable, I think all will agree that it was the engineer. The engineer, as a rule, is a modest fellow, so modest in fact and so averse to publicity of any kind that, referring to him as a class, he was hardly occupying the place he should in public estimation before the war. By way of illustration, in the early history of a mine in Bisbee, the chief owner was also the proprietor of a saloon and spent most of his time there. When asked why he did not pay more attention to the mine, lie replied: "Oh! I can hire a boy to look after that; it takes a man to run this bar." Comparisons of the position and pay of engineers with other occupations are sometimes made to show that the engineer is not getting all that he should, considering the time of preparation and the qualifications required. Perhaps at least a part of the cause may be his aloofness from many of the practical affairs of everyday life. Whether he won the war or not, the part played by the engineer has certainly placed him on a sort of pedestal in the public estimation at present and it is very desirable to keep him there and maintain the position he has made for himself.

Jan 9, 1919

By M. S. Burton, B. W. Christ, G. V. Smith

Evidence of the effects which high-angle grain boundaries and veining subgrain boundaries have on the yield phenomenon of zone-refined iron is reported. Room-temperature tensile tests on 50-mil wive at several gram sizes produced upon recrystallization at diffevent temperatures below 910C (a-y phase-transfornzatzon temperature) show that upper and lower yield stress decrease with increasing grain size. The upper yield point effectively disappears at grain sizes of 81 and 102 u in samples of this diameter. However, samples of 129 p grain size. produced during recrys-tallization at 950°C, exhibit a pronounced upper yield point and an increased lower yield stress. Possible causes of the reversal in the grain-size dependence of yielding are discussed. Veining substructure, detected with picval-HC1 etchant, but not with 2 pct nital, is formed during the a-y transformation, and is believed to account for the observed effecls. The strengthening associated with high-angle boundaries in zone-refined tron is discussed in terms of: 1) the stress dependence of slzp multiplicity, and 2) the stress dependence of dislocation emission from grain boundaries. WIDE use of transmission electron microscopy and dislocation etch-pitting techniques has led to a growing awareness of the presence of dislocation substructures in annealed pure metals. Whereas much speculation'-4 has developed about the influence which subgrain structures have on the mechanical behavior of metals, particularly the yield strength, only limited experimental evidence correlating subgrain structures with lower yield strength has been presented. 2,3,5-7 It is the purpose of this note to present experimental evidence of the effects which grain boundaries and subgrain boundaries have on both the upper and lower yield strength of zone-refined iron. Effects due to high-angle boundaries formed upon recrystallization below the a-y phase transformation are compared with effects due to veining subgrain boundaries formed upon "recrystallization" above the a-y phase-transformation temperature. These effects are further compared with the reported influence 2,3,5-7 which low-angle boundaries have on the lower yield strength of bcc transition metals. EXPERIMENTAL PROCEDURE The starting material for these experiments was a 1-in.-diam zone-refined ingot prepared at Battelle Memorial Institute. Initial purification of electrolytic iron by vacuum-induction melting was improved by a floating zone-melting treatment in ultrapure hydrogen.' Chemical analysis of this zone-refined iron appears in Table I. Tensile samples of 50-mil wire were prepared by rolling and drawing portions of the ingot. An intermediate recrystallization anneal at 625°C after rolling to a reduction in area of 85 pct was carried out in an evacuated Vycor capsule (10-=5 mm Hg). Further reduction in area of 91 pct was followed by recrystallization in evacuated Vycor capsules at temperatures between 600" and 950°C, see Table 111. All samples

Jan 1, 1967

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods' for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

By AIME AIME

BECAUSE of its unequalled skill, your country in- creased its production until, in 1913, it produced 40 per cent. of the world's consumption of coal, iron ore, and cast iron; 45 per cent. of the steel; and 60 per cent. of the copper. Your industrial effort, in a general manner and your mining effort in particular, has been tremendous. In the general economy of the world, you occupy an incomparable position of power and action. All your curves of production, mineralogical, metallurgical, financial, commercial, have taken terrific trigonometrical tangents and you will easily under- stand the sorry position of your competitors. I must, therefore, pay a tribute of homage arid admiration to you all who, each in his sphere, have been the artisans of such prosperity and my earnest wish is that you continue in this way.

Jan 1, 1920

By Yves Dardel

The literature concerning the remelting of alunlinum and its alloys is very rich. Unfortunately the majority of the papers on this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges, and the atmosphere of the furnaces bring into the bath during the successive remelt-ings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, or others, if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H², O2, H²O, co², CO, CH,, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of sieverts3 as a function of its partial pressure PH2 in the atmosphere m = K vPH² [I] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Rijntgen and Braun4, RÖntgen and M611er5, Bircum-shaw6 and Winterhagerl have rendered it possible to determine the value of K, when the temperature is less than 1.000°C. One obtains: log K = - 4,702.5T + o 238 [2] Besides its usual significance, the term Ph~ represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is1 when no gas exchange Occurs between the two phases, the Pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary Occurs, the quantity of H² should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature decreases, the internal pressure of H² increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a a depending On the hydro- static pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However1 even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1949

By Frank W. Clinard, Oleg D. Sherby

The effect of multiple an transformations on diffusion in a dilute iron alloy was studied. Inter-penetration between iron and an Fe-Co alloy was evaluated, under thermal-cycling conditions chosen so as to transform only the iron-rich side of the diffusion couple. It is shown that a small but consistent diffusion enhancement by a factor of two results when data from the transforming side of thermally cycled specimens are compared with predicted inter diffusion coefficients based on isothermal data. No enhancement is found when data from the mntransforming side of such couples are compared with predicted diffusivities. It is suggested that short-circuiting by moving pain boundaries is the most likely mechanism contributing to the observed diffusion enhancement from multiple phase transJormations in iron. Transformation-induced Point defects, dislocation-pifie short-circuiting, and point defects generated by dislocation motion are less effective in contributing to enhanced diffusion under the experimental conditions utilized. SO far as is known, no studies have been made of the effect of allotropic transformation on diffusion. previous to this investigation. Studies have been made, however, of the influence of transformation on the diffusion-controlled processes of spheroidization and sintering. Cullen1 has described a method of accelerating spheroidization in an AISI 1030 steel. Partial transformation between a and ? phases was uti-

Jan 1, 1965

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By H. F. Yancey, O. L. Furse

For several years the Bureau of Mines at its Northwest Experiment Station, in cooperation with the Mines Department. of the University of Washington, has been studying the breakage and degradation of coal. The first phase of the study was devoted to the determination of the friability of many coals of various ranks and comparison of various methods for estimating friability.' A study of the relative ease or difficulty with which various coals are reduced to the fine size required for use as pulverized fuel followed the completion of this work. Baltzer and Hudson2 list twelve research organizations in the United States, two in England, one in Germany and one in Canada that are reported to be engaged on this problem; showing the general appreciation of the need for a simple method of estimating the grindability of different coals. Hardgrove,3 ho has advanced a method for estimating grindability, points out that pulverizer tests of different coals are incomplete and unsatisfactory. He compares such tests to that of a boiler test made without knowledge of the calorific value of the coal. Frisch arid Holder4 also stress the same point. They state that,

Jan 1, 1934

By W. H. Bassett

IN the commercial annealing of cartridge brass there are four points regarding which definite data are essential. They have to do with the correct interpretation of grain count in its relation to annealing temperature and, incidentally, to Brinell hardness. These points are: 1. The comparison of the grain sizes of two cartridge-brass mixtures: 69 copper, 31 zinc, 0.376-in. (9.5-min.) gage; and 68 copper, 32 zinc, 0.130-in. (3.3-mm.) gage. 2. The comparison of the grain sizes of annealed metal that had previously been reduced by rolling varying amounts; for instance, 20.0, 36.6, 50.9, and 59.1 per cent. 3. The determination of standards for grain sizes on annealed brass of the composition 68 per cent. copper, 32 per cent. zinc and 69 copper, 31 zinc. 4. The comparison of grain size with Brinell hardness on identical samples of annealed metal. In their comprehensive and thorough investigation of the recrystallization of cold-worked alpha brass on annealing,1 Mathewson and Phillips have discussed the relations between temperature of anneal, degree of deformation, and structural alteration in alpha brass. They have also shown certain comparisons between the ordinary physical properties and the grain size of annealed brass. The purpose of the present investigation is mainly concerned with the grain size of cartridge brass, its relation to Brinell hardness, and the publication of sufficient data to enable those engaged in the inspection of such material to have a correct foundation upon which to work.

Jan 1, 1919

By Francis M. Walters

IN spite of the war and the preoccupation of many physical metallurgists with work on secret or confidential problems, definite progress was made during 1944 in our understanding of the behavior of steel and of the effect of alloying elements. During the first two years of the war there was much concern over the possible unavailability of certain alloying elements; this period saw the development of the N.E. (National Emergency) steels. However, the measures taken eased the alloy situation and currently, highly practical problems under study are the graphitization of low-carbon steel and weld-cracking, while investigations of more theoretical interest have concerned hardenability, isothermal reactions, the effect of hydrogen and the interpretation of the notched-bar impact test.

Jan 1, 1945

By G. M. Schwartz, D. M. Davidson

THE Duluth gabbro outcrops containing sulphides of copper, nickel, and iron are located on both sides of State Highway No. 1 an airline distance of 8.5 miles southeast of Ely in northeastern Minnesota. The region of known sulphide occurrences includes parts of sections 5, T. 61 N., R. 11 W., and parts of sections 25, 26, 32, 33, and 34, T. 62 N., R. 11 W. These sections, given in Fig. 1, are all in Lake County, Minnesota. Part of the area, which lies entirely within the Superior National Forest, is shown on the topographic map of the Ely quadrangle. The original discovery was made in 1948 when a small pit was opened in weathered gabbro rubble for use on a forest access road. A shear zone had caused unusual decomposition in this glaciated area, and the resulting copper stain was noted by Fred S. Childers, Sr., an Ely prospector, who began searching the outcrops along the base of the intrusive. He was joined in further exploration by Roger V. Whiteside of Duluth. In the summer of 1951 a small diamond drill was moved into the area and a hole 188 ft deep was drilled, passing through 11 ft of glacial drift into sulphide-bearing gabbro. This paper is a preliminary report on the geology of the newly discovered ore. The Duluth gabbro is one of the largest known basic intrusives and may be defined as a lopolith.1 It extends northeastward from the city of Duluth as a great crescent-shaped mass that intersects the shore of Lake Superior again near Hovland, 130 miles to the northeast, see Fig. 2. The distance around the outside of the crescent is nearly 170 miles. The form of the intrusive is simple at Duluth where it ends abruptly north of the St. Louis River; at the east end, however, the gabbro splits into two elongated, sill-like masses separated mainly by lava flows and characterized by minor irregularities. The outcrop reaches a maximum width in the central part where it is about 30 miles across, and a maximum thickness of about 50,000 ft. It may be significant that the sulphides occur at the base of the thickest part. The lopolith has segregated into rock types ranging from peridotite to granite. The most abundant types are olivine gabbro, gabbro, troctolite, anorthosite, and granite. Of lesser importance quantitatively are peridotite, norite, pyroxenite, magnetite gabbro, and titaniferous magnetite. Grout estimates that two-thirds of the gabbro at Duluth is olivine gabbro. Variations in the percentages of plagioclase, augite, olivine, and magnetite-ilmenite constitute the only essential differences found among the basic rock types. The predominant mineral is plagioclase, mainly labradorite. Plagioclase and olivine seem to have crystallized early, and the olivine rich rocks, usually troctolite, are found in the lower part. Segregations of titaniferous magnetite are abundant near the base of the gabbro along the eastern part and also occur far above the base. These have recently been described in detail by Grout' Near the top, segregation has produced a gradation to granite, or "red rock," as it is known locally. This consists of quartz, red feldspar, and hornblende. The red rock forms a. zone with a maximum width of nearly 5 miles but is quantitatively unimportant from Duluth northward for 35 miles. In Cook county, where the gabbro splits, each of the two sill-like masses has a red rock top somewhat thicker in proportion to the gabbro below than in the main central mass. The intrusive ranges from coarse to medium in grain size and from granitoid to diabasic in texture. Throughout much of the Duluth gabbro in Minnesota banding and foliation are well developed, as Grout has emphasized! The bands are mainly a result of variation in the percentage of minerals, as in troctolite with alternating bands high in olivine and in plagioclase. A few bands may consist largely of one mineral, as is true of some segregations of magnetite. Many of the banded rocks show a clearly developed parallelism of platy plagioclase crystals, and both banding and foliation are believed to conform to the floor of the lopolith. Throughout its extent in Minnesota the Duluth gabbro dips east and south toward Lake Superior. It is generally believed to extend beneath Lake Superior and is found as a smaller mass exposed along the north side of the Gogebic district in Wisconsin and Michigan. The dip at and near the base ranges along most of its length from 20 to 40°, but at places the internal banding dips even more steeply. The dip of the upper part is much less, and if it is assumed that the flows along the north shore of Lake Superior are a dependable indication, it does not exceed 15º. The formations shown in Table I which are intruded by the gabbro range from Keewatin to Middle Keweenawan in age. They present a significant picture. At the top, the gabbro and its accompanying

Jan 1, 1952