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By C. G. Dunn

With respect to theories of recrystalliza-tion in metals plastically deformed. it has been said that the present status of this subject is far from satisfactory.1 It may also be said that before any mechanism of recrystallization for metals and alloys can be set forth in a satisfactory manner, there must be made available considerable data on orientation changes that occur during the deformation and recrystallization processes. Although extensive data have been published on recrystallization in single crystals and in poly-crystalline specimens, more results of a type that can be classified according to simple orientation changes would be desirable in this complex field. It might even be said that before classifications are made according to types of orientation changes, it may be possible to classify a considerable amount of data into certain kinds of orientation states if groups of common or nearly common orientation occur. Methods for computing the probability of occurrence for various types of groups have been published2 and it has been pointed out in particular that it should be possible to analyze orientation data for high-order twin relationships between old and new grains even when agreement is not at all exact. In this connection, work on recrystallization in silicon ferrite reported in a paper concerned with complex groups of annealing twins3 indicated that some data were consistent with primary nucleation OCcurring according to a second-order or a third-order twin transformation. However, further work in this latter direction was definitely needed. It is, therefore, the purpose of the present paper to report data and analyses for primary nucleation in silicon ferrite following small deformations that have been carried Out at the Pittsfield Works' Laboratory of the General Electric Co. Analyses have been made with the aid of standard groups of twins that are reported elsewhere.4 PReparation oF Specimens and Experimental Procedure The material used in the present investigation was taken from the same heat of steel as that .used in a prior report.3 The finished strip in both cases was made by the Allegheny-Ludlum Steel Corporation according to methods that produce a high degree of preferred crystal orientation. Samples with large grains had the following composition: 3.45 per cent Si, 0.003 C, 0.008 P, 0.020 S, 0,075 Mn, 0.03I A1 and 0.072 Cu. Thickness of specimens was 0.012 inches. Plastic deformation was produced by cold-rolling the samples on a mill with 8-in. diameter rolls, the plane of the sample in each case coinciding with an XY plane (the plane of projection for the stereo-graphic plots) and the elongation occurring in the X direction. In general, elongations were held to about 3 or 4 per cent.

Jan 1, 1945

By Henry H. Logan

THE purpose of mine-hoist safety controllers is to prevent hoists from being operated at speeds above those considered safe and expedient, to ensure proper acceleration and retardation near the ends of travel, and to prevent overwinding. In other words, they are to safeguard the normal speeds and movements of the hoisting drums and cages. The object of this paper is to explain the fundamental principles of hoist controllers, and to aid in their selection, installation, and maintenance. There have been many designs of mechanical hoist controllers, the basic elements of which as ultimately developed consisted of a flyball governor and another movable member supported by a frame and arranged to move in a vertical, horizontal, or rotary direction, depending upon the particular design, the whole mechanism arranged to be driven in synchronism with the hoist drum. In case of overspeeding, inadequate retardation, or overwinding, a pawl or catch controlled by the governor would engage teeth or dogs on the moving member, which through mechanical connections would cut off the power and set the brakes. Since in strictly mechanical hoist controllers valuable time was lost while the various mechanical movements took place, an important development was the invention of controllers partly mechanical and partly electrical. This type of controller has a governor and movable cams to be driven in synchronism with the hoist drum, the governor representing the hoist speeds and the cams profiled to form a pattern for retardation, representing the travel of the cages in the shaft. This type is also provided with an overspeed switch and usually with a pair of selective-limit switches, one for the top limit and the other for the bottom. In overspeeding or failure to retard in accordance with the profile of the cam, the overspeed switch will be opened, or if the top or bottom limit is overrun one of the limit switches will be opened, breaking the retaining circuit of a contactor or magnetic latch, causing the power to be cut off and the brakes applied. When the speed falls to the predetermined safe speed, the overspeed switch closes, and a hoist equipped with power-operated brakes controlled in emergency by a solenoid-operated valve can be restarted immediately by simply moving the master control lever to the "off" position and then applying power-unless brake interlocks are used, in which case the brake lever or levers must also be brought to the "applied" position, after which the hoist can be restarted in the usual way. When hand-reset weights instead of solenoid-operated mechanism are arranged to set the brakes for emergency, it is necessary to reset the weights manually, besides bringing the master control lever to the "off" position before the hoist can be restarted. Should a final limit be slightly overrun, and a stop made with a limit switch held open by a cam, it is necessary for the hoistman to use a "backing-out" switch which short-circuits the overrun limit switch, reestablishing the hoist-control circuit, and simultaneously opening the

Jan 1, 1940

By R. A. Young

Zinc metal production in the operating plants in the United States during 1948 was approximately equal to that of the year 1947, although new developments during the year assure higher output in 1949, if economic conditions are favorable. In the Western plants, the man-power shortage was almost completely overcome and new capacity has been or is in the process of being added to three plants; thus by December of 1948 daily zinc metal production had risen to the highest point since May of 1944 despite strikes in one large primary smelter and in one secondary plant.

Jan 1, 1949

By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.'-' It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer' has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953

T. Kirke Rose, London, Eng. (communication to the Secretary*) :—The authors have shown that, under certain conditions, the rate of dissolution of gold by chlorine and bromine is reduced by the addition of 10 per cent. of silver to the gold, and that the action is almost stopped when the silver amounts to 30 or 40 per cent. of the alloy. Even if full recognition is given to the practical way in which the work was done, however, it is to be regretted that Prof. Hofman and Mr. Magnusou did not determine the temperature at which the experiments were carried out. From the details given, it may be inferred that the temperature was raised by chemical action by about 20' C. when 21 g. of sulphuric acid was added, and that the mixture was then slowly cooled down during the experiment. When bromine or very weak chlorine solutions were used, there could not have been any perceptible heating-action. As the action of both chlorine and bromine is aided by heat, it follows that the stronger solutions of chlorine were given an unfair advantage over the weaker solutions, and over bromine. If the temperature had been the same in each case, I do not think that the conclusions deduced by Prof. Hofman and Mr. Magnuson' would have been found to be justified. (This is speaking generally. In barrel-treatment the conditions are similar to those in the experiments.) The superior speed of bromine as compared with chlorine at equivalent strengths is not yet disproved, and the differences noted between strong and weak solutions of chlorine may have been largely a function of the temperature. Moreover, the authors used somewhat-coarse particles of gold, and did not try how far time was a factor, although it is obvi-

Jan 1, 1906

Alfred E. Hunt, Pittsburgh, Pa. (communication to the Secretary): Mr. Blue's statement (page 576) that, " owing to the presence of iron and other impurities, makers of aluminum. assert that native corundum is unsuited for the production of that metal," is somewhat incorrect, at least so far as it may refer to any objection made by the officials of the Pittsburgh Reduction Co. to the Canadian corundums. We recognize corundum as among the richest and purest of the ores of aluminum, and the material furnished from Canada would offer for us the advantage of a supply near to our works for the manufacture of aluminum at Niagara Falls. The real difficulty which we find in the use of corundum for this manufacture is the cost of the raw material as compared with that of native bauxites. In this item we include not only, the price of the corundum as it has been offered to us, but also the expense of grinding it to an impalpable powder, which must be done before it can be used directly in the manufacture of aluminum, and the cost of preliminary chemical treatment for purification—which latter operation, however, is also required for bauxite. I agree with Mr. Blue that the introduction of new and irnproved processes has greatly reduced, during the past ten years, the cost of manufacturing aluminum; but I am inclined to believe that any further improvements, facilitating the use of corundum for this purpose, would apply, in equal or greater degree, to the common clays (silicates of aluminum) which exist in all parts of the world, are more easily mined and handled, and are likely to be always cheaper per unit of aluminum than any corundum.

Jan 1, 1899

By Emil Gathmann

(San Francisco Meeting, September, 1915) THROUGH wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," -i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot: Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe .at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium,

Jan 8, 1915

By P. L. De Bruyn, R. J. Charles

The transfer of kinetic energy of translation into other forms of energy by impact is a fundamental process in most crushing and grinding operations. During and after the impact process the original source energy may be accounted for in any of the following possible forms: 1) Kinetic energy of translation of both the impacted and impacting objects. 2) Kinetic energy of vibration of the components of the impact system. 3) Potential energy as strain energy of the components of the system or in the form of residual stresses. 4) Heat generated by internal friction during plastic deformation or during damping of elastic waves. 5) New surface energy of fractured materials. At any instant during the impact process only the strain energy of the components of the system can contribute directly to the brittle fracture process. If fracture is the desired result, as in comminution, it would seem advantageous to choose or arrange the conditions of impact so that a maximum amount of the original kinetic energy could be converted to strain energy at some moment during a single impact. The present work deals with determination of these desirable conditions for a simple case of impact and application of the principles involved to general cases of impact.

Jan 1, 1956

By Joseph Jensen

California's outstanding contribution to unit operation is the plan of development now established for the North dome of the Kettleman Hills. Beginning April 1, 1931, the Kettleman North Dome Assn. will control the unified operation and development of 10,800 acres of proven and semiproven oil land, and at the same time the Standard Oil CO. of California will operate as another unit its fee land of 9460 acres of similar character. The holdings of the two companies are in a checkerboard mile-square pattern. In addition to this, 410 acres of land may yet be included in the Kettleman North Dome Assn. unit and 530 acres of land are definitely out of both units. The owners of some of this land have expressed their intention of cooperating in a reasonable way with these two units. Cooperative agreements are now in force as to most of this field. Under the definitions of a unit pool and a near-unit pool,' the operation at Kettleman Hills will be a near-unit operation, but because of the size of the structure and its proven highly productive character, the arrangement. concluded on Jan. 31, 1931, in the approval of the Kettleman North Dome Assn. Agreement by Secretary of the Interior Ray Lyman Wilbur and by California State Oil and Gas Supervisor R. D. Bush is of outstanding importance to the entire oil industry. No other major unit operation plans are under way in California at the present time. There has been some little discussion of a plan in the North Belridge field and a feeling that the discovery of oil in the Lost Hills field and also in the South Belridge field would necessitate consideration of unit plans. So few data are available for these areas, as to the land that should be included in such unit plans, that little constructive action is now possible. The beginning of drilling on the Middle dome of the Kettleman Hills also makes it an area deserving consideration for unit operation. All four of the above-named areas lie on the west side of the San Joaquin Valley, in Kings and Kern counties, to the south of the

Jan 1, 1931

US 4,135,913-Extraction of nickel values from iron-containing nickel sulfide ore, particularly pentlandite or nickeliferous pyrrhotite A mixture of raw ore, roasted ore, or iron powder, and coal as a reductant is heated to a temperature of 800- 1000° C in a nonoxidizing atmosphere to convert the bulk of the iron content to metallic iron while diffusing into the iron the bulk of the nickel, the mixture cooled, and the cool material separated into a magnetic fraction containing most of the nickel and a non-magnetic gangue fraction A Illis arid L S Renzoni, assigned to International Nickel Co, Inc Jan 23, 1979 7 pp (75-21) Filed 10-10-75 (621,343) Priority Canada, 10-27-72 (155,032) Same Canadian 981,910, dated Jan 20, 1976 Same British 1,389,145, dated Apr 3, 1975 US 4,135,917-In the recovery of gallium from a solution obtained by the digestion of bauxite or nepheline in an alkali solution for the production of alumina, the digestion solution is neutralized, the neutralized solution evaporated to an op¬timum caustic alkali concentration and adjusted to a ratio of alkali metal oxide to alumina of above 2, the corrected solu¬tion contacted with a gallium-aluminum alloy, arid high-purity gallium recovered from the solution by electrolysis or cemen¬tation K A Badaliants, et al Jan 23, 1979 6 pp (75-109) Filed 12-19-77 (862,201) Priority USSR, 12-22-76 (2,428,¬006) US 4,135,918-Extraction of copper from copper sulfide ore containing also one or more of the metals iron, nickel, arid cobalt Ore is roasted at a temperature of 750-800° C to expel sulfur, the sulfur-free calcine slurried in water containing a sufficient amount of sulfuric acid to supplement any sulfuric acid formed in situ, the slurry heated at 150-165° C in the presence of a reducing gas to form soluble sulfates of metals other than copper while reducing copper to elemental form, arid the slurry filtered to recover copper solids Any precious metals present in the ore will report with the copper solids V A Ettel, A P Devuyst, R Sridhar, arid C. E O'Neill, as¬signed to International Nickel Co, Inc Jan 23, 1979 5 pp (75-117) Filed 3-2-78 (882,610) Priority Canada, 5-13-77 (278,360)

Jan 1, 1980

By Perry Olcott

The Texas Gulf Coast had a rather disappointing year in the type of oil fields found. Although 17 fields were found in the area during the year, as against 21 fields in 1938, no field of major proportion was discovered. Of these 17 fields, 11 were oil fields, 4 were gas and distillate fields, and 2 were gas fields. The wildcat activity for the year resulted in about 400 dry holes, although probably 10 per cent of these were edge wells close to proved areas. During the year, 1455 oil and gas wells were completed as compared to 1637 wells in 1938, a decrease of 11 per cent. Production for the Texas Gulf Coast area for the year was 100,253,937 bbl. as against 92,530,467 bbl. produced in 1938, an increase of 8 per cent. The daily average production was 274,668 bbl. for the 365 days in the year, although only 252 producing days were allowed by the Railroad Commission; that is, 69 per cent of the time as compared to 71 days shut in for 80 per cent of the time producing in 1938. The total number of oil and distillate wells producing at the end of 1939 was 9495 as against 8451 at the end of 1938—an increase of 1044 wells, or 12 per cent. Of these wells, 6547 were flowing and 2948 pumping, or 69 per cent flowing. At the end of the previous year, 66 per cent of the wells were flowing. New Fields Angleton, Brazoria County.—The Angleton field was discovered by the completion of Glen McCarthy's No. 1 Carr in October for an initial production of 180 bbl. a day of 50" gravity oil through 11/64-in. choke with 3400 Ib. on tubing. The field is 1½ miles east of the town of Anchor. The discovery undoubtedly can be credited to the reflection seismograph, since several companies worked the area from 1933 onward with this type of exploration. The principal block was taken by the Humble company in 1934. Two deep holes by Humble revealed the presence of structure, although both were dry. The Humble and Sun companies later contributed money and acreage toward the drilling of the discovery well. The production is from a sand in the Frio, about 1700 ft.

Jan 1, 1940

By Perry Olcott

The Texas Gulf Coast had a rather disappointing year in the type of oil fields found. Although 17 fields were found in the area during the year, as against 21 fields in 1938, no field of major proportion was discovered. Of these 17 fields, 11 were oil fields, 4 were gas and distillate fields, and 2 were gas fields. The wildcat activity for the year resulted in about 400 dry holes, although probably 10 per cent of these were edge wells close to proved areas. During the year, 1455 oil and gas wells were completed as compared to 1637 wells in 1938, a decrease of 11 per cent. Production for the Texas Gulf Coast area for the year was 100,253,937 bbl. as against 92,530,467 bbl. produced in 1938, an increase of 8 per cent. The daily average production was 274,668 bbl. for the 365 days in the year, although only 252 producing days were allowed by the Railroad Commission; that is, 69 per cent of the time as compared to 71 days shut in for 80 per cent of the time producing in 1938. The total number of oil and distillate wells producing at the end of 1939 was 9495 as against 8451 at the end of 1938—an increase of 1044 wells, or 12 per cent. Of these wells, 6547 were flowing and 2948 pumping, or 69 per cent flowing. At the end of the previous year, 66 per cent of the wells were flowing. New Fields Angleton, Brazoria County.—The Angleton field was discovered by the completion of Glen McCarthy's No. 1 Carr in October for an initial production of 180 bbl. a day of 50" gravity oil through 11/64-in. choke with 3400 Ib. on tubing. The field is 1½ miles east of the town of Anchor. The discovery undoubtedly can be credited to the reflection seismograph, since several companies worked the area from 1933 onward with this type of exploration. The principal block was taken by the Humble company in 1934. Two deep holes by Humble revealed the presence of structure, although both were dry. The Humble and Sun companies later contributed money and acreage toward the drilling of the discovery well. The production is from a sand in the Frio, about 1700 ft.

Jan 1, 1940

By John Garcia

IN some districts of the bituminous coal field the problem of construct-ing bulkheads to seal off water under pressure is becoming increasingly important. Recently this matter has been brought very much to the front by the loss of a large. Illinois mine due to failure of a bulkhead that separated it from several old, flooded mines. As this great misfortune has provoked much inquiry about proper bulkhead design, it is felt that a description of the successful and extensive water-sealing practice at three mines that have different natural conditions will be of considerable interest to those connected with properties having a present or future water problem and to engineers that may have to design safe bulkheads of economical construction. These three mines are the Saxton acid Dresser, near Terre Haute, Ind., and the Hegeler, near Danville, 111. All three have water conditions that make it necessary to regularly seal off till worked-out sections of the mine, and there are considerably over a hundred bulkheads in each. As far as the writers know, these three mines are the only ones in the bitu-minous coal fields of the United States with anything like so large a number of water seals and experience, although a number of other mines are known to have a few bulkheads. More detail will he included herein on the Saxton mine than on the others, as the writers are more familiar with it.

Jan 1, 1937

By Bradley Stoughton, Henry M. Howe

This paper presents an experimental verification of some of the predictions made by one of us1 concerning the influence of certain conditions of casting upon the size and position of the pipe, and the position of the segregate, in steel ingots. The predictions which we have been able to verify are the following: A. That the pipe is shortened and the segregate raised: 1. By slow casting; 2. By casting with the large end up instead of down; 3. By retarding the cooling of the top, e.g., by means of a sinking-head. B. That the pipe is shortened by slow cooling. C. That the pipe and segregate lie in the last-freezing part. Our procedure was to cast ingots of wax (commercially pure stearic acid) containing a little bright green copper oleate (usually 1.5 per cent.) under varying conditions; to saw each ingot open along a longitudinal plane passing through its axis; and to examine the longitudinal section thus laid bare. In order to make the segregate or enriched part more distinct in color from the impoverished part, a very little red cerasine was added. An experiment which will be described later showed that the cerasine itself does not segregate markedly, if at all. Hence we may assume that the strong contrasts between the green and red shown in so many of our ingots are due, not to segregation of cerasine, but to that of the green oleate, in the wax which in itself is uniformly reddened with cerasine.

Jan 1, 1908

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.'" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By M. E. Nicholson

The solubility of carbon in Ni-Cu alloys was determined at 1000°C. The factors which limit solid solubility are discussed with particular reference to the influence of electronic factors. The results indicate the extent of solid solubility is a function of the density of states at the Fermi surface. THE solid solubility of an interstitial element is primarily limited according to Seybolt and Fullman1 and Speiser and Spretnak2 by (a) the strain energy produced when the solute atom takes its interstitial position, and (b) the partial molal free energies of the solid solution and the coexisting phases. In several binary systems of a transition and a noble metal, where there are no abrupt changes in strain energy or free energies of coexisting phases, the solid solubility of an interstitial third element drops abruptly to a negligible value at a composition corresponding to a complete filling of the "d-band." Such a decrease occurs in the case of hydrogen in the Pd-Ag system at 60 pct Ag.3,4 The solubility of carbon in Ni-Cu alloys seems to vary in a similar manner as indicated by the embrittling effect of carbon on these alloys. These al- loys are embrittled by slow cooling due to the precipitation of graphite. This embrittlement can be removed by heat treatment if the carbon content is less than the solid solubility limit at the heat-treating temperature. If the carbon content of the alloy exceeds the solid solubility at the heat-treating given temperxture, the embrittlement cannot be eliminated by solution heat treatment.' Since pure nickel has a carbon solubility of 0.25 wt pct6 at 1000°C, embrittlement is easily removed from commercial nickel and nickel-rich alloys, which may contain of the order of 0.10 wt pct C. Embrittlement due to carbon cannot be removed from Ni-Cu alloys containing 70 to 80 wt pct Cu by annealing unless: the carbon content is of the order of 0.04 wt pct CL or less."' Thus, it appears that the

Jan 1, 1962

By L. A. Updegraff

Before discussing the application of capacitance for the measurement of moisture content in a moving stream of coal it might be well to first give a brief description of the process and then show how it can be applied to the coal industry. A capacitor may be described as a device having two conductors separated by an insulator, the conductors hereafter being designated as a test cell or test plates and the insulator as the dielectric. Capacitance, therefore, is a measure of the ability of a capacitor to store an electrical charge. Two basic factors that affect capacitance are the dimensions of the capacitor and the dielectric constant of the insulator. Capacitor dimensions which affect its capacity are the area A of the conductive surface, and the distance d between plates. Capacitance is inversely proportional to the distance between plates and directly proportional to area A, so if capacitance is indicated as C and the dielectric constant as K the equation for capacitance would be C = AK/d. The dielectric constant can be described as the ratio of the actual capacitance of any given material to that of a vacuum, which is unity. In industrial applications the area of the plates remains constant as also does the distance between them, leaving the dielectric constant as the only variable to affect the capacitance measurement. Figure 1 is a schematic diagram of an r-f excited capacitance bridge in which a test cell is part of the circuit. This bridge consists of four capacitors in two pairs connected across an a-c voltage source. In one side of the circuit the two capacitors are fixed but in the other side they are variable, one being the rebalance capacitor operated by the servo motor and the other the test plates between which the dielectric passes. Capacity of the plates is a function of the dielectric constant of the material between them and is measured at radio frequency. Within the recording instrument is an r-f oscillator and a 60 c ps modulator. The radio frequency signal is generated by the oscillator, modulated by a 60 cps wave, and sent to the bridge. Therefore the signal entering the capacitive bridge is a radio frequency carrier with a 60 cycle envelope, If the bridge is in balance as the signal enters there would be no voltage drop and so no output by the detector. As long as the dielectric constant remains the same the bridge will stay in balance. However, any change in the dielectric constant, which in this case would be a change in moisture content, would affect the bridge. Higher moisture increases the capacity of the test cell which causes less voltage to develop across it causing imbalance of the bridge. This in turn causes a radio frequency signal to appear at the detector. Output from the detector is a 60 cycle ripple which is in proportion to the imbalance of the circuit. A 60 cycle amplifier boosts the detector signal to enough power to drive the servo motor which positions the recording pen and also rotates the variable capacitor, to which it is mechanically connected, to bring the bridge back in balance. An increase in moisture causes the servo motor to rotate in one direction, but a decrease causes imbalance in the opposite direction, and thus rotates the motor in that direction. This brings the bridge back in balance and stops the motor. The bridge shown in Figure 1 has been modified so as to provide a wide range of adjustments. Coarse and fine span adjustments located in the recording instrument are set to govern the amount of pen movement for a given change in capacitance. A measuring head unit contains coarse and fine zero adjustments for

Jan 1, 1961

By P. Somasundaran, D. R. Nagaraj

This study initiated to explore the potential of commercial chelating extractant for beneficiation of minerals revealed "LIX "65N to be an excellent collector for cuprite and chrysocolla. The collector action of the LIX is proposed to result from its chelation with copper species on the surface of the minerals. Thus, the syn-isomer of LIX65N, which is unable to form a chelate with copper ions, failed also to act as a collector. The proposed mechanism takes into account partitioning of LIX between the mineral surface (to form a surface chelate) and the copper chelate dispersed in the bulk aqueous phase (either due to formation of the chelate with dissolved copper, or due to detachment of chelate formed at surface). The efficiency of the collection is dependent upon this partitioning since the bulk chelate is found unable to collect. The marked decrease in flotation obtained when copper was added to the system supports this mechanism. The dependence of flotation of chrysocolla and cuprite on pH and reagentizing time is discussed on the basis of the proposed mechanism. Batch laboratory flotation tests using synthetic mixtures of oxide, sulfide and mixed oxide-sulfide copper minerals with quartz demonstrated the ability of LIX to separate the copper minerals from quartz.

Jan 1, 1980

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually average about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment. Surface deposits contain sulphur in the same range of concentrations as the salt dome deposits, i.e., from 10 to 50 pct sulphur, associated with various gangue materials such as silica, limestone, and gypsum. The pirincipal distinction, then, does not lie in the percentage of sulphur contained in the ore, but in the geological nature of the deposit. A recent study' of the world sulphur supply situation estimated 1950 sulphur production in the free world countries at 5.6 million long tons, of which the United States produced 5.2 million tons, or 93 pct of the total. While America's domestic needs alone would have been covered by national production, about 1.4 million tons were exported during the same year. Despite all the steps which are being taken to restrict use of elemental sulphur and to force the fullest possible development of alternate sulphur sources here and abroad, the deficit in elemental sulphur production will probably increase with time. As a result of intensive prospecting for oil throughout the Gulf Coast area discovery of significant new salt domes is held unlikely. With the growing scarcity of sulphur and what appears to be an inevitable rise in price, recovery from deposits not amenable to Frasch-process mining assumes greater economic importance. Untapped Reserves The most important deposits in this category are located in Sicily, where elemental sulphur occurs in Miocene limestone and gypsum formation. Sulphur content of these ores ranges from 12 to 50 pct with an estimated average of 26 pct. Although quantitative estimate of these reserves is not available it is held that they exceed 50 million tons of sulphur. Similar deposits occur also on the mainland which contribute about one-third of Italy's total current annual production of 230,000 tons, but these are known to be nearing exhaustion. Significant surface deposits of volcanic origin are located in South America, Japan and western United States, silica being characteristic gangue con-stituent. The largest of these deposits are in South America. More than 100 extend over a zone 3000 miles long, paralleling the west coast of South America. 'Total sulphur content of these deposits has been estimated to be as high as 100 million tons. The main islands of Japan also possess at least 40 known volcanic sulphur deposits with probable reserves of 25 to 50 million tons.' Prospected reserves in western United States might amount to 2 million long tons, principal deposits being located in the northwestern part of Wyoming, southern Utah, and eastern California. Volcanic deposits of lesser importance are found around the Mediterranean, in Turkey and Greece, and in Africa, Egypt, Abyssinia, and Somaliland. Beneficiation Methods Different methods of beneficiation have been used in these various locations. In Italy the Calcarone kiln and Gill regenerative furnaces are used exclusively. Both utilize heat liberated by burning part of the sulphur in the ore to liquify or vaporize the remaining sulphur, which is recovered by solidification or condensation. The Calcarone kiln is of conical shape, generally 35 ft in diam at base and 18 ft high. A kiln of 25,000 cu ft capacity burns for about two months and yields about 200 tons of sulphur. The Gill furnace consists of a series of chambers with domed roofs. Sulphur is burned and melted in one chamber at a time and the hot combustion gases are used to preheat the ore charge in the subsequent cell. These furnaces operate on a cycle of 4 to 8 days. The recovery yield of both systems is about 65 pct. Sulphur losses amount to 25 pct through the combustion to sulphur dioxide; about 10 pct is retained in discarded calcines. Ores containing less than 20 pct are not considered suitable as furnace feed. These methods are not only wasteful because of the low recovery obtained, but represent a serious atmospheric pollution problem. Sulphur produced ranges from 96 to 99 pct purity and thus does not match Texas or Louisiana sulphur. Owing to the present shortage, sulphur in the Middle East sells

Jan 1, 1954