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By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By AIME AIME

A PAPER prepared by James A. Adams, development engineer of the fitline & Smelter Supply Co., and presented at the last Annual Meeting of the A.I.M.E. in New York City, de- scribed a new automatic pulp density controller which has had a most favorable reception. Manual control has until now been the universal practice in spite of its shortcomings; samples of pulp for density determination were often improperly taken, and only at the operator's convenience, so that the trend in density changes was frequently missed, and the grinding circuit al- lowed to operate under something less than the most efficient conditions.

Jan 1, 1940

By C. Q. Payne

(New York Meeting, February, 1912.) THE art of crushing ores and other materials by means of rolls is a comparatively recent one. While the first record of rolls using iron crushing-surfaces dates back to the year 1806, when they were employed in Cornwall, their principal development has taken place during the last 30 years. To Stephen R. Krom belongs the credit of the pioneer in introducing the belted high-speed roll, which has had its origin and a marked development in this country. His notable contribution to the art was in the use of a single bed-plate or frame supporting the roll-shafts, and to which levers holding the movable roll-bearings were pivoted. He also made use of steel tension-rods to support the crushing-strains, and of hammered-steel tires for the crushing-surfaces. These changes brought the design of crushing-rolls to a high level. Following closely thereon, about 1885, W. R. Eckart conceived the idea of the swivel or ball-and-socket support for the roll-shaft bearings. This is an excellent mechanical conception, especially for bearings held against a spring pressure, and while it may not be necessary for all types of rolls, yet it has been quite generally adopted by other roll-designers, and illustrates the refinement which roll-construction has now reached. Other engineers, as for example, Argall, Vezin, Roger, and Sturtevant, to mention only a few among many, have also given the closest attention to the various details of rolls, such as the frame, springs, bearings, and shafts, and have developed many novel and original designs. It has remained, however, for the boldness and originality of Mr. Edison to extend the field of crushing-rolls in two new directions, and to cause them to exercise new functions. In developing crushing-machinery for his Portland cement works, Mr. Edison constructed ? giant " rolls, having a diameter of 6 ft. and a length of. face of 7 ft.

Jun 1, 1912

By E. R. Gilbert

Klopp et al. have reported data on tensile and creep properties of are-melted and electron-beam-melted tungsten. We would like to point out some similarities between their creep results and ours on are-melted and powder-metallurgy tungstenand offer some alternate interpretations of the data which lead to different rate-controlling mechanisms. Klopp et al. observed extensive transient creep in the 2250" to 3500°F temperature range where the acthetivation energy is 106,400 ± 3300 cal mole-1. They suggest cross slip as the possible rate-controlling mechanism since "cross slip may occur only by the movement of screw dislocations, and not edge dislocations, thus allowing only partial recovery of the strain hardening and resulting in a continuously decreasing creep rate, characteristic of transient creep.'' Our tests on are-melted tungsten and powder-metallurgy tungsten displayed an extensive transient creep stage in the same temperature range but they also displayed a steady-state creep stage. The stress levels and strain rates of the two investigations, 1.4 to 7 kg mm-2 and 10-7 to 10-4 sec-1 for that of Klopp et al. and 4.5 to 10 kg mm-2 and 10-8 to 10-4 sec-1 for those of Gilbert et al., are overlapping. The activation energy for creep of our powder-metallurgy tungsten is 105,000 cal mole-1. This close agreement with the value found by Klopp et al. suggests that the same mechanism may be common to both types of materials. It may be possible to gain some additional insight into the rate-controlling mechanism by applying the analysis made by conrad22 in terms of the activation volume. The value for the activation volume depends upon the dislocation mechanism and may be used to help differentiate between various dislocation mechanisms. The activation volume for cross slip is 10 to 100 b3. Values determined from our data were 130 to 220 b3 which are in better agreement with the range of 102 to 104 b3 for nonconservative motion of jogs. Values determined from data of Klopp et al. are 240 to 1040 b3. We suggest that the rate-controlling mechanism for creep in this temperature range may be nonconservative motion of jogs assisted by enhanced diffusion along grain boundaries or dislocations. This model requires an activation energy lower than that for self-diffusion as is observed. If this is the controlling mechanism, a higher activation energy which is closer to that for self-diffusion might be expected for tests conducted on specimens with reduced grain boundary area, i.e., larger grain size. In support of this premise we have conducted tests on speci- mens having one to three grains per cross section for which a higher activation energy of 130,000 cal mole-1 was observed. Also, in agreement with results of Klopp et al., a faster creep rate resulted from the increased grain size and probable decreased dislocation density. Further argument against the cross slip mechanism is based on the constant activation energy we obsserved over the range of 5.0 to 10 kg mm-2,21 whereas the activation energy for cross slip displays a significant stress dependence.23 In addition to this, the powe on the stress term for the strain-rate dependence appears too high for cross slip. The values for tungsten fall in the range of 4.5 to 7 (Klopp et al. and Ref. 21) whereas values of approximately 2 are observed in creep by cross slip for hep metals.24 At temperatures from 3300° to 4000°F, Klopp et al. observed an activation energy of 141,000 ± 4000 cal mole-' which is less than that for self-diffusion, 153,000 cal mole-1, 25 and less than that reported for high-temperature creep of powder-metallurgy tungsten by Green:' 160,000 cal mole-1. Klopp et al. suggested that recovery of strain hardening by dislocation climb is the rate-controlling mechanism in this temperature region. Actually an activation energy larger than that for self-diffusion is predicted by this model if the temperature dependence of the elastic modulus27 is taken into consideration. Klopp et al. attributed this lack of correlation to the compositional differences between powder-metallurgy tungsten used by Green and their own arc- and EB-melted tungsten. It is our position that the value of 141,000 ± 4000 cal mole-' represents a transitional value between the higher and lower activation energies and does not represent a discrete mechanism of deformation. If the tests had been extended to higher temperatures the higher value of activation energy would have been observed as has been demonstrated by both our analy sis'' of isothermal test data by GE-NMPO28 and differential temperature tests28 on are-melted tungsten. The activation energies determined (170,000 and 160,000 cal mole-1) were greater than that for self-diffusion and are in better agreement with the value found by Green. The model of dislocation climb is associated with ; activation volume of 1 b3 according to Conrad.22 The activation volume calculated for the creep data of fou independent investigators in the temperature range where the activation energy for creep is near that for self-diffusion (Klopp et al. and Refs. 26, 28, and 30) is 110 to 2800 b3 and is in the range suggested for nonconservative motion of jogs. In the case of tungsten this mechanism may be preferred over that of dislocation climb. Sincere appreciation is expressed to Messrs. J. E. Flinn and F. L. Yaggee for the helpful discussions and suggestions in the preparation of this communication.

Jan 1, 1967

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

In the Ti-Cd system two intermediate phases, TiCd and Ti Cd, have been found and characterized by X-ray diffraction powder techniques. An earlier reference' had reported the existence of the compound Tisd. No structural details, however, were given nor was there any indication of the possible existence of other binary compounds. Studies of the solubility of titanium in liquid cadmium2 led to the discovery of both TiCd and Tisd. The solid phase in equilibrium with saturated solutions of titanium in liquid cadmium at temperatures below 620°C is TiCd, whereas TizCd is the equilibrium solid phase above 620°C. Both thermal analysis and X-ray studies show that a peritectic reaction between the y phase (~isd) and cadmium to form the 6 phase (Ti Cd) occurs at 620°C. X-ray diffraction powder photographs of material isolated from the ingots used in the solubility measurements as well as material prepared by a direct heat of the appropriate stoichiometric amounts of titanium and cadmium can be indexed on the basis of a tetragonal unit cell with a = 2.904 ± 0.002A, co = 8.954 * 0.004A, c/a = 3.083. No variation of lattice parameters indicative of a range of composition is evident. With four atoms in the unit cell the calculated density of the intermetallic is 7.05 g per cm3; the observed value is 7.07 g per cm3. The TiCd lattice is primitive as indicated by the fact that there are no systematic absences among hkl reflections. The absence of all hko reflections for which h + k = 2n + 1 is also evident. This systematic absence indicates the following two space groups, C\h — P4/n and D&~4/nmm; both groups, however, have the same two- and four-fold positions. Stoichiometry, symmetry and space group indicate two likely structure types. They are the PbO-litharge3 (B10) type and the Ti CU (B11) type. Spatial considerations favor the B11 structure with atoms placed in the following positions: 2Ti (c) 0, 1/2, Z; l/2, 0, Z 2Cd(c) 0, 1/2, Z; 1/2, 0, Z The TiCd structure may be summarily described as a layered structure in which double cadmium layers alternate with double titanium layers along the c-axis. The best agreement between calculated and observed intensities is obtained for the values ZTi = 0.608 and ZCd = 0.130. Calculated and observed powder intensities as well as other pertinent powder data are recorded in Table I. Interatomic distances for the proposed structure are recorded in Table II and are to be compared with the distances of closest approach for titanium and cad-

Jan 1, 1962

By D. Harrington

ANNUAL or necessary inspections and investigations of coal mines for various purposes were made possible through the Federal Coal Mine Inspection Act of May 7, 1941, which authorized entry to the Secretary of the Interior through the Bureau of Mines. Primary object of these inspections is to obtain information pertaining to health and safety conditions. Among the purposes for which the data are to be used, are annual reports to Congress, the publication of inspection reports, and the compilation and publication of statistics. The act states that inspections and investigations shall be made by employees of the Bureau of Mines, who shall co-operate with other bureaus of the U. S. Department of the Interior, as well as with the official mine-inspection, safety cr health agencies of the several states and territories. The act specifies that a coal-mine inspector shall have "the basic qualifica-

Jan 1, 1946

By Molly Gleiser, John Chipman

The standard free energy of formation of WC was obtained from determination of the equilibrium WC + CO2 = W + 2CO between 1215° and 1266°K. Its uallie is -8340 * 300 cal Per mole over the above range of temperature. AS a part of a program devoted to measuring the stabilities of the carbides, a study was made of the free energy of formation of tungsten carbide, WC. The homogeneity range of this compound is very small,' and it is generally accepted and is dealt with here as a stoichiometric compound. The heat of formation, ?H°f, of WC has been accurately measured by Huff, Squitieri, and snyder.2 The only attempt, however, to measure the free energy of formation of this compound was made by Schenck, Kurzen, and wesselkock3 who brought tungsten carbides into equilibrium with H2 and CH4. Unfortunately their results are not sufficiently accurate nor consistent enough to permit the calculation of free energies. METHOD Heating mixtures of tungsten and carbon powders in hydrogen for 4 days at 1050°C led to formation of some WC without any trace of W2C. It was deduced, therefore, that at least below this temperature W2C will not be formed during experiments with mixtures of tungsten and WC. This was subsequently shown to be correct. The method chosen was the measurement of the equilibrium of the reaction

Jan 1, 1962

By John N. Dew, William L. Martin, `

This paper describes the results of a laboratory investigation conducted to obtain data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. Air and fuel requirements, rates of advance, com-bustion temperatures, and coke and fluid distributions are presented. The mechanism of oil recovery by in stiu combustion is discussed. Five crude oils ranging in gravity from 10.9 to 34.2"' API were prodrrced from a semiadiabatic, uncon-.solidnted sand pack by in situ combustion. Experimental conditions were varied over a wide range in order to determine the inter-relation-.ships of process variables. The mini-mum air flux requirement for self-sustained combustion was found to he less than 10 scf/hr-ft'l. The rate of advance of a self-sustained combustion zone was found to be nearly proportional to the air flux at the combustion front. The effects of presrure and injected air flux were studied in a series of experiments using a 21.2" API crude. A minimum air require-ment was observed at an air .flux of 20 scf/hr-ft'. The oil saturation con-sumed as fuel averaged 5.5 per cent of pore volume. The effect of air pressure was, found to be .small for experiments having high combustion eficiencies. This study should promote a better understanding of the problems and mechanisms involved in labora-tory investigations and field applications of the in situ combustion pro-cess. The data presented will be use- ful in the interpretation of results of field tests. When tempered with volu-metric sweep efficiencies, the data can be used in making preliminary economic appraisals of the process as applied to reservoirs containing high porosity unconsolidated media. INTRODUCTION The purpose of this work was to obtain laboratory data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. In situ combustion basically consists of (1) injecting air into a reservoir through selected input wells to create an air sweep through the reservoir, (2) igniting the crude at the injection well, and (3) propagating the combustion front through the reservoir by continued air injection. By this means, oil is swept toward producing wells in the area. The fuel for combustion is supplied by heavy residual material (coke) which has been deposited on the sand grains during distillation and cracking of the crude oil ahead of the combustion front. Recovery of petroleum by a combustion or heat wave process is not a new idea. F. A. Howard was granted a patent in 1923 on a process in which air and a combustible gas were pumped into an injection well and ignited.' Russian engineers reported on field experiments with a crude oil gasification process in 1935'. Other known early field tests include those conducted near Bar-tlesville and Ardmore, Okla., in 1942." More recently completed field tests include an inverted seven-spot by Sinclair Oil Co. in the Delaware-Childers field, Nowata County, Okla.'; a three-well and an inverted five-spot test by Magnolia Petroleum Co. in Jefferson County, Okla."."; and a test by California Research Corp. in the Irvine-Furnace field in Kentucky. The Worthington Corp. has completed a test in cooperation with the Forest Oil Corp. in Clark County, 111.l Several field tests are now in progress. Sinclair has acquired a 600-acre lease in the Humboldt-Chanute field, Allen County, Kans., and is under way with a large-scale operation. Three field tests are under way in California. The General Petroleum Corp. is conducting an inverted five-spot pattern test in the South Bel-ridge field in Kern County under a cooperative agreement with 11 other companies, including Continental Oil Co. California Research Corp. is conducting a four-well pattern test in Midway-Sunset field near Maricopa, and Richfield Oil Corp. is under way with a test in the Ojai field in Ventura County. Although the published information is valuable concerning results of field tests, little laboratory data other than that reported by Kuhn and Koch5 are available to aid in appraising the tests from a technical or economic standpoint. Engineering data needed to evaluate the process include the amount of air required per barrel of oil recovered, minimum injection rates which will support combustion, rates of advance, air required per unit volume of reservoir cleaned, amount of oil recovered, and amount of oil consumed as fuel. The present laboratory investigation was undertaken to provide these data for that portion of the reservoir swept by the combustion zone. The first phase of this investigation was exploratory in nature and was conducted at injection pressures less than 100 psig. Data were ob-

By C. T. Holland

This discussion is concerned with those com-J- paratively infrequent bumps that eject material from the failed mass with enough energy to wreck heavy machinery and seriously injure or kill people. In such cases there is a loud report, and the pressure waves set up in the mine atmosphere wreck ventilation controls several hundred feet from the site of the failure. Vibrations are induced in the earth's crust which may be detected several miles from the point of origin, and explosive gases may be released in large quantities." Usually a dense suspension of dust is produced from the failed mass, together with dust placed in suspension by the resulting air blast. These rock bursts or bumps have also been called mountain shots, bounces, pillar bursts, and crumps. Such occurrences, when extensive, are serious catastrophes, and may force abandonment of the mine.' CAUSES OF ROCK BURSTS Rock bursts in coal mines have occurred in sev-eral places under diverse geological conditions, mining methods, and/or practices. A study of many such occurrences indicates that they depend on the following conditions: 1) cover thickness of 500 ft or more, 2) cover composed of strong members and having a strong member lying close to or on the coal bed, and 3) a floor that does not readily heave. The minimum thickness of cover under which coal mine rock bursts occur is based on observation. Under unusual circumstances involving very strong roof members and/or mining systems, and/or practices especially likely to induce bursts, a burst conceivably could occur under less roof. Under special circumstances rock bursts have occurred in marble quarries almost at the surface.' Furthermore, under very heavy cover it is likely that controlling roof members need not be as strong and as close to the coal bed to cause bumps. Just what constitutes a strong roof or roof member is open to question. Obviously the strength of a roof member is determined by its thickness, the distance between bedding planes across which little or no bond exists, the spacing and development of joints, and the inherent strength of the rock material. Strata sections showing roofs under which rock bursts in coal mines have developed are illustrated in Fig. 2. In several instances the strength of rocks composing the roof of mines developing bumps has been tested. The tests (Table I) show that these rocks develop considerable strength in compression, bending, and shear and that in some cases the strengths are very high. No quantitative data are available concerning joints in roof members over coal beds where rock bursts have occurred, but the author has examined many mines subject to bursts and has received the impression that joints in the shales immediately over the coal beds are always present and well developed. In the main sandstone or conglomerate members themselves, however, where observed, he has yet to see a fracture system indicating well developed joints. Undoubtedly joints are present, but the evidence indicates that they are few, poorly developed, and widely spaced. In a mine subject to bumps, moreover, actual measurements of roof spans up to 225 ft between supports under a cover of about 800 ft have been made before roof failure occurred. Such spans signify strong roof. In coal beds subject to rock bursts, the bottom rock is usually a sandy shale. A few tests (Table I) have been made on the floor rock of coal beds. Observations in mines indicate that they are usually weaker than roof rocks and that under load they show more plastic effects. Observation in ground subject to bursts invariably indicates a relatively strong floor highly resistant to heaving, although some heaving may occur. Other factors listed as favorable to rock bursts are: 1) mountainous surface; 2) steeply dipping beds; 3) proximity of faults, folds, and other similar geologic structures. Many bursts have occurred in mines under mountainous country, although many bursts in mines under a surface with little relief indicate that thickness of cover, not relief, is the essential factor. In steeply dipping beds, many bursts occur in mines that are essentially flat, and rock bursts have been recorded in beds dipping as much as 35o Most rock bursts in the U. S. occur in beds that dip less than 10 pct. It is also true that most U. S. coal is produced from beds dipping less than 10 pct. Geologically, faults are regarded as providing stress relief, but in the vicinity of faults, as well as sharp folds, it would seem that residual stresses could be present. The fact that rock bursts occur in areas remote from faults and sharp folds suggests that their presence is not necessary for this phenomenon to take place. There have been many bursts close to faults and folds, and it may be assumed that occasionally such structures accentuate their occurrence3 The conditions and circumstances under which they occur, coupled with the effects produced, leave In the Crowsnest Pass coalfield, British Columbia, a rock burst is estimated to have released 1.8 million cu ft of methane.

Jan 1, 1959

[Executive E. DEGOLYER, Chairman SYDNEY H. BALL WILLIAM H. Bassett RICHARD PETERS, JR. J. V. W. REYNDERS Finance GEORGE D. BARRON, Chairman H. A. GUESS GEORGE OTIS SMITH]

Jan 1, 1928

By Haydn H. Murray, Sam H. Patterson

The term "clay" is somewhat ambiguous un¬less specifically defined, because it is used in three ways: (1) as a diverse group of fine-¬grained minerals, (2) as a rock term, and (3) as a particle-size term. Actually, most persons using the term "clay" realize that it has several meanings, and in most instances they define it. As a rock term, clay is difficult to define be¬cause of the wide variety of materials that com¬pose it; therefore, the definition must be gen¬eral. Clay is a natural earthy, fine-grained ma¬terial composed largely of a group of crystalline minerals known as the clay minerals. These minerals are hydrous silicates composed mainly of silica, alumina, and water. Several of these minerals also contain appreciable quantities of iron, alkalies, and alkaline earths. Many defini¬tions state that a clay is plastic when wet. Most clay materials do have this property, but some clays are not plastic; for example, halloysite and flint clay. As a particle-size term, clay is used for the category that includes the smallest particles. The maximum-size particles in the clay-size grade are defined differently on various grade scales, Soil investigators and mineralogists gen¬erally use 2 micrometers as the maximum size, whereas the widely used scale by Wentworth (1922) defines clay as material finer than ap¬proximately 4 micrometers. Some authorities find it convenient to use the term "clay" for any fine-grained, natural, earthy, argillaceous material (Grim, 1968). When used this way, the term includes clay, shale, or ar¬gillite, and some argillaceous soils. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, the term is generally un¬derstood by those who use it. Clay is an abun¬dant natural raw material, and it has an amaz¬ing variety of uses and properties which will be discussed in this chapter. Clays rank among the leading industrial min¬erals in both tonnages produced and total value. Their importance is indicated in Table 1, which lists the 1970, 1971, and 1972 production and values according to the U.S. Bureau of Mines (Ampian, 1972). Adequate reliable statistical data on which to summarize world production of clay are un¬available; this paragraph outlines the world re¬quirements for clay only in a very general way. According to one estimate, the world bentonite production in 1972 was 3.5 million tons (Anon., 1973a), but in the authors' opinion it was prob¬ably at least 5 million tons. The total fuller's earth produced was at least 1.5 million tons and may have been as much as 2 million tons. The total world kaolin production in 1972 was more than 10 million tons. Approximately 7 million tons of this total was produced in only two regions-the Georgia-South Carolina kaolin belt in the United States and the Cornwall re¬gion, United Kingdom. The world's 1972 out¬put of ball clay, which is also produced pri¬marily in the United States and the United Kingdom, was approximately 1.5 million tons or perhaps a little more. The total world fire clay production in 1972 was probably about one and one-half to two times and the miscellaneous clay production three times the United States production. As industrial minerals, clays are a complex group that consists of several mineral commodi¬ties, each having somewhat different mineral¬ogy, geologic occurrence, technology, and uses. In this chapter these commodities are organized

Jan 1, 1975

Sailing westward from the Society Islands in the fall of 1774, England's noted explorer Captain James Cook discovered New Caledonia-that long, linear island that has played such an important and varied role in the history of nickel. Upon his return to England the following year, Cook's announcement of this uncharted island generated governmental interest, but its distance from the Island Empire, the troubles in the colonies, and the difficulties with France combined to keep English interest indirect and in the background of the then-current events.

Jan 10, 1968

By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.' Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By Bunting S. Crocker

PEBBLE grinding at Lake Shore is not a temporary wartime substitute. The tube milling plant, with a 1000 ton per day capacity, grinds a hard siliceous ore to 90 pct - 325 mesh. The plant, prior to using pebbles, was consuming 4.3 lb of 1 1/4-in. grinding balls per ton of ore, which amounted to 785 tons of balls per year. At September 1951 prices, $132.60 per ton, this steel cost amounted to, $104,400 per year, or $0.285 per ton milled. By the Lake Shore method of substituting screened rock for this steel, all of this cost is saved. This is one of the major economies in Lake Shore mill practice. Regardless of the ultimate price of grinding balls, a change, back to steel balls is not considered. The present pebble plant is more flexible than a steel ball plant and equally efficient. For example, if it is desired to change the size of grinding media, the pebble charge in any mill can be changed completely in 4 to 5 days, as against 76 days to change completely a 1 1/4-in. steel ball charge. To change pebble size it is necessary only to change two sets-of screens and clean out the rock feed storage bin. This will take 8 to 10 days as against 3 to 4 months to clean. out the customary supply of grinding balls kept on hand. Also it has not always been ' possible to purchase all desired sizes of balls at any price. In an analysis of savings effected by the use of the pebble mills, the flexibility of the Lake Shore grinding plant should be discussed, as it has a direct bearing on these savings. The plant has always used several units to handle tonnage rather than sending all the tonnage through a single unit. This principle may result in using small diameter mills, but no objection to that is seen. At no time has any advantage been found in cost per ton ground in large diameter mills. Both the capacity and the power of any mill varies as the diameter raised to the 2.6th power. Consequently large or small mills are equally efficient, and a plant should be designed to use as many units-or combination of units as is consistent with reasonable operating practice. Mills under 5 ft diam are harder to reline, etc. To define the case at Lake Shore, .2600 tons per day formerly were milled in seven 7x6-ft ball mills and twelve 5x16-ft (and two 6x16-ft) tube mills.* This gave an excellent test plant. and an extremely efficient-one. In this plant the ratio of ball mills to tube mills was 1: 2. When the much cheaper pebble mills were substituted for the tube mills, this. ratio -was changed to one ball mill to four pebble mills to take the greatest possible advantage of the cheaper operating mill, i.e., the pebble mill. This flexibility without loss in efficiency has been an important item in the cost savings. It is interesting to note that the use of pebbles for fine grinding was. proved first in the laboratory in a 12-in. ball mill. In fact, since 1934 all testing on -.8 mesh material has been done in this 12-in. mill. Scope of the Tests A paper on fine grinding at Lake Shore Mines was published in July 1940.1 This paper covered 7 years of intensive research on fine grinding as well as sizing methods and equipment, plant scale grinding tests on 5x16-ft tube mills with and without .grate discharges-both with 1 1/4-in. and 3/4-in. balls, the use of laboratory mills to evaluate plant changes, and several reports on classifiers and classification. In the following July the addendum report' was added in which the idea of series-circuit grinding was introduced, and the results of running five stages of tube mills and bowl classifiers were shown. Since 1940, the ball milling end of the plant has been altered extensively as a result of tests on the use of 3 1/2-in. rods in 7x6-ft mills and the use of the Tyler repulping screen with from 7 to 14 mesh screens. These tests are, lengthy and may be covered in a separate 'report later. The scope of this report is confined to ore ground by rod milling and ball milling until it passed through an 8 mesh Tyler Ty-rod screen. The -8 mesh screen undersize then was pumped to a primary bowl classifier in open circuit and the sands .from the bowl sent to the primary pebble mills, see Fig: 1. In the pebble mill circuit the ore is ground to 90 pct -325 mesh (24 pct + 28 microns) In studying the flowsheet, attention should be paid to the efficiency of the classification equipment used. The Tyler repulping screen is an efficient machine on the 8 to 10 mesh separation, and the bowl classifier is equally efficient at the 325 mesh separation. Efficient classification is a necessity for series-circuit stage grinding. The ore is hard siliceous porphyry, 60 pct SiO2, 80 pct insoluble. Its grindability at different. meshes has been shown near the top of 'the list in F. C. Bond's grindability tests' Lake Shore is not shown, but an adjacent-mine with identical ore, Wright-Hargreaves, is. Reasons for the-Changeover Since 1936 grinding balls have been rising steadily in price with no sign of stopping. For a mill that used 4.5 to 5.2 lb of grinding balls for every ton of ore ground this rise represented an alarming increase in grinding costs. In many cases the quality of the grinding balls fell off as the scrap steel became more difficult to obtain. The ratio of tube mills to ball mills increased with the use of the Tyler repulping screen in the ball mill circuit. Originally only 3.0 lb of balls per ton were used in the tube mills, and this

Jan 1, 1952

By F. Claisse, R. Angers

Self-diffusion in iron has been measured during rapid a-r transformations using a variant of the Kryukou and Zhukhovitskii diffusion method. The study was performed by thermally cycling iron foils (1 to 6 cpm) through the transformation (=910°C). Some foils have been subjected to over 1000 cycles and some have spent more than 15 pct of their total diffusion time in the process of transformation. The experimental results show that the a-r transformation has no measurable effect on self-diffusion in iron. The study is completed by a quantitative analysis of mechanisms which can affect the diffusion rate during the transformation. The analysis confirms the experimental results. SINCE diffusion is an important factor in many solid-state transformations, it is of interest to study how it is affected by the stresses generated during these transformations. Clinard and Sherby1'2 were the first to make a study along these lines. They measured diffusion coefficients in Fe-FeCoV couples subjected to slow thermal cycling (1.5 cph) through the a-r transformation range. They found an enhancement of diffusion by a factor of about two. The purpose of the present paper is to report measurements of the self-diffusion coefficient of iron during much more rapid thermal cyclings (1 to 6 cpm) through the a-r transformation (-910°C). These more rapid cyclings produce higher strain rates during the transformation and should emphasize any possible influence of transformation upon diffusion. EXPERIMENTAL Iron foils, 25 to 35 µ thick, were cold-rolled from 99.92 pct pure iron and annealed in pure helium for 2 hr at 870°C; the resulting grain diameter was about 150 µ. Specimens 0.5 by 8 cm were cut from the foils and I7e55 was vapor deposited on one of their surfaces. A 38 gage alumel-chrome1 thermocouple was spot welded in the middle of one of the specimen long edges, Fig. 1. Two 38 gage chrome1 wires were also spot welded along the same edge on each side of the thermocouple; they were placed 2.5 cm apart and used for electrical resistance measurements. In order to prevent twisting and crumpling, the specimens were pinched between two quartz plates 0.1 by 1 by 7 cm and the assembly was close fitted into a 1 cm ID quartz tube. Four holes were drilled through the tube to let the 38 gage wires out: these were connected to the recording equipment by means of extension wires. 20-gage nickel wires fixed at both ends of the specimens were used to thermally cycle the foils by Joule heating. The above described device was placed in a 2.7 cm ID quartz tube which in turn was placed in a tubular furnace. Either a pure helium atmosphere or circulating hydrogen was used during the experiments. Specimens were subjected to thermal cycles between a minimum temperature To and a maximum temperature Tm at rates ranging from 1 to 6 cpm. This was obtained by maintaining the furnace at a constant temperature near the minimum temperature To and periodically passing an electric current through the specimen. Cooling was achieved by heat losses to the surroundings. The forms and periods of cycles were varied from one specimen to another; however, each specimen was subjected to one type of cycle only. The temperature and electrical resistance variations of the specimens were recorded as a function of time. The temperature curves were used for diffusion calculations while the electrical resistance curves were used to monitor the transformation and to determine its starting point and its approximate duration. Diffusion was measured by the method developed by Kryukov and zhukhovitskii3 and modified by Angers and Claisse.4,5 In this method a metallic foil is coated on one side with a radioactive isotope and the activity is measured periodically on both sides during the diffusion anneal. The following equation then holds: where: I1 Activity on the surface on which the deposit is made. I, Activity on the opposite surface. t Diffusion time. B Constant. D Diffusion coefficient. d Foil thickness including the deposit. G(t) A function of time; it is a second order correction term which is given graphically in Refs. 4 and 5. The diffusion coefficient D is found by plotting ln[(Il - I2)/(I1 + I,)] -G(t) against t; the resulting slope m leads to an accurate calculation of D through Eq. [2]. The effect of the a-r transformation on diffusion is expressed by the ratio DT/DU where:

Jan 1, 1970

By Bunting S. Crocker

EBBLE grinding at Lake Shore is not a temporary BlE wartime substitute. The tube milling plant, with a 1000 ton per day capacity, grinds a hard siliceous ore to 90 pct — 325 mesh. The plant, prior to using pebbles, was consuming 4.3 lb of 11/4-in. grinding balls per ton of ore, which amounted to 785 tons of balls per year. At September 1951 prices, $132.60 per ton, this steel cost amounted to $104,400 per year, or $0.285 per ton milled. By the Lake Shore method of substituting screened rock for this steel, all of this cost is saved. This is one of the major economies in Lake Shore mill practice. Regardless of the ultimate price of grinding balls, a change back to steel balls is not considered. The present pebble plant is more flexible than a steel ball plant and equally efficient. For example, if it is desired to change the size of grinding media, the pebble charge in any mill can be changed completely in 4 to 5 days, as against 76 days to change completely a 1-in. steel ball charge. To change pebble size it is necessary only to change two sets of screens and clean out the rock feed storage bin. This will take 8 to 10 days as against 3 to 4 months to clean out the customary supply of grinding balls kept on hand. Also it has not always been possible to purchase all desired sizes of balls at any price. In an analysis of savings effected by the use of the pebble mills, the flexibility of the Lake Shore grinding plant should be discussed, as it has a direct bearing on these savings. The plant has always used several units to handle tonnage rather than sending all the tonnage through a single unit. This principle may result in using small diameter mills, but no objection to that is seen. At no time has any advantage been found in cost per ton ground in large diameter mills. Both the capacity and the power of any mill varies as the diameter raised to the 2.6th power. Consequently large or small mills are equally efficient, and a plant, should be designed to use as many units or combination of units as is consistent with reasonable operating practice. Mills under 5 ft diam are harder to reline, etc. To define the case at Lake Shore, 2600 tons per day formerly were milled in seven 7x6-ft ball mills and twelve 5x16-ft (and two 6x16-ft) tube mills.* This gave an excellent test plant and an extremely efficient one. In this plant the ratio of ball mills to tube mills was 1:2. When the much cheaper pebble mills were substituted for the tube mills, this ratio was changed to one ball mill to four pebble mills to take the greatest possible advantage of the cheaper operating mill, i.e., the pebble mill. This flexibility without loss in efficiency has been an important item in the cost savings. It is interesting to note that the use of pebbles for fine grinding was proved first in the laboratory in a 12-in. ball mill. In fact, since 1934 all testing on — 8 mesh material has been done in this 12-in. mill. Scope of the Tests A paper on fine grinding at Lake Shore Mines was published in July 1940.' This paper covered 7 years of intensive research on fine grinding as well as sizing methods and equipment, plant scale grinding tests on 5x16-ft tube mills with and without grate discharges both with 1-in. and -in. balls, the use of laboratory mills to evaluate plant changes, and several reports on classifiers and classification. In the following July the addendum report2 was added in which the idea of series-circuit grinding was introduced, and the results of running five stages of tube mills and bowl classifiers were shown. Since 1940, the ball milling end of the plant has been altered extensively as a result of tests on the use of 3-in. rods in 7x6-ft mills and the use of the Tyler repulping screen with from 7 to 14 mesh screens. These tests are lengthy and may be covered in a separate report later. The scope of this report is confined to ore ground by rod milling and ball milling until it passed through an 8 mesh Tyler Ty-rod screen. The —8 mesh screen undersize then was pumped to a primary bowl classifier in open circuit and the sands from the bowl sent to the primary pebble mills, see Fig. 1. In the pebble mill circuit the ore is ground to 90 pct —325 mesh (24 pct + 28 microns). In studying the flowsheet, attention should be paid to the efficiency of the classification equipment used. The Tyler repulping screen is an efficient machine on the 8 to 10 mesh separation, and the bowl classifier is equally efficient at the 325 mesh separation. Efficient classification is a necessity for series-circuit stage grinding. The ore is hard siliceous porphyry, 60 pct SiO,, 80 pct insoluble. Its grindability at different meshes has been shown near the top of the list in F. C. Bond's grindability tests.' Lake Shore is not shown, but an adjacent mine with identical ore, Wright-Hargreaves, is. Reasons for the Changeover Since 1936 grinding balls have been rising steadily in price with no sign of stopping. For a mill that used 4.5 to 5.2 lb of grinding balls for every ton of ore ground this rise represented an alarming increase in grinding costs. In many cases the quality of the grinding balls fell off as the scrap steel became more difficult to obtain. The ratio of tube mills to ball mills increased with the use of the Tyler repulping screen in the ball mill circuit. Originally only 3.0 lb of balls per ton were used in the tube mills, and this

Jan 1, 1953

By Bunting S. Crocker

EBBLE grinding at Lake Shore is not a temporary BlE wartime substitute. The tube milling plant, with a 1000 ton per day capacity, grinds a hard siliceous ore to 90 pct — 325 mesh. The plant, prior to using pebbles, was consuming 4.3 lb of 11/4-in. grinding balls per ton of ore, which amounted to 785 tons of balls per year. At September 1951 prices, $132.60 per ton, this steel cost amounted to $104,400 per year, or $0.285 per ton milled. By the Lake Shore method of substituting screened rock for this steel, all of this cost is saved. This is one of the major economies in Lake Shore mill practice. Regardless of the ultimate price of grinding balls, a change back to steel balls is not considered. The present pebble plant is more flexible than a steel ball plant and equally efficient. For example, if it is desired to change the size of grinding media, the pebble charge in any mill can be changed completely in 4 to 5 days, as against 76 days to change completely a 1-in. steel ball charge. To change pebble size it is necessary only to change two sets of screens and clean out the rock feed storage bin. This will take 8 to 10 days as against 3 to 4 months to clean out the customary supply of grinding balls kept on hand. Also it has not always been possible to purchase all desired sizes of balls at any price. In an analysis of savings effected by the use of the pebble mills, the flexibility of the Lake Shore grinding plant should be discussed, as it has a direct bearing on these savings. The plant has always used several units to handle tonnage rather than sending all the tonnage through a single unit. This principle may result in using small diameter mills, but no objection to that is seen. At no time has any advantage been found in cost per ton ground in large diameter mills. Both the capacity and the power of any mill varies as the diameter raised to the 2.6th power. Consequently large or small mills are equally efficient, and a plant, should be designed to use as many units or combination of units as is consistent with reasonable operating practice. Mills under 5 ft diam are harder to reline, etc. To define the case at Lake Shore, 2600 tons per day formerly were milled in seven 7x6-ft ball mills and twelve 5x16-ft (and two 6x16-ft) tube mills.* This gave an excellent test plant and an extremely efficient one. In this plant the ratio of ball mills to tube mills was 1:2. When the much cheaper pebble mills were substituted for the tube mills, this ratio was changed to one ball mill to four pebble mills to take the greatest possible advantage of the cheaper operating mill, i.e., the pebble mill. This flexibility without loss in efficiency has been an important item in the cost savings. It is interesting to note that the use of pebbles for fine grinding was proved first in the laboratory in a 12-in. ball mill. In fact, since 1934 all testing on — 8 mesh material has been done in this 12-in. mill. Scope of the Tests A paper on fine grinding at Lake Shore Mines was published in July 1940.' This paper covered 7 years of intensive research on fine grinding as well as sizing methods and equipment, plant scale grinding tests on 5x16-ft tube mills with and without grate discharges both with 1-in. and -in. balls, the use of laboratory mills to evaluate plant changes, and several reports on classifiers and classification. In the following July the addendum report2 was added in which the idea of series-circuit grinding was introduced, and the results of running five stages of tube mills and bowl classifiers were shown. Since 1940, the ball milling end of the plant has been altered extensively as a result of tests on the use of 3-in. rods in 7x6-ft mills and the use of the Tyler repulping screen with from 7 to 14 mesh screens. These tests are lengthy and may be covered in a separate report later. The scope of this report is confined to ore ground by rod milling and ball milling until it passed through an 8 mesh Tyler Ty-rod screen. The —8 mesh screen undersize then was pumped to a primary bowl classifier in open circuit and the sands from the bowl sent to the primary pebble mills, see Fig. 1. In the pebble mill circuit the ore is ground to 90 pct —325 mesh (24 pct + 28 microns). In studying the flowsheet, attention should be paid to the efficiency of the classification equipment used. The Tyler repulping screen is an efficient machine on the 8 to 10 mesh separation, and the bowl classifier is equally efficient at the 325 mesh separation. Efficient classification is a necessity for series-circuit stage grinding. The ore is hard siliceous porphyry, 60 pct SiO,, 80 pct insoluble. Its grindability at different meshes has been shown near the top of the list in F. C. Bond's grindability tests.' Lake Shore is not shown, but an adjacent mine with identical ore, Wright-Hargreaves, is. Reasons for the Changeover Since 1936 grinding balls have been rising steadily in price with no sign of stopping. For a mill that used 4.5 to 5.2 lb of grinding balls for every ton of ore ground this rise represented an alarming increase in grinding costs. In many cases the quality of the grinding balls fell off as the scrap steel became more difficult to obtain. The ratio of tube mills to ball mills increased with the use of the Tyler repulping screen in the ball mill circuit. Originally only 3.0 lb of balls per ton were used in the tube mills, and this

Jan 1, 1953

By Richard L. Ashbrook, John F. Wallace

Several high-temperature eutectics of cobalt and nickel alloys were modified by small additions of selected elements. Thes-e alloys were compared to unmodified melts for microstructural variations. A few modified compositions were selected on the basis of structure and their tensile and stress-rupture behavior determined. The results of stress-rupture tests in air at 1800 F and room-temperature tensile tests of four high-temperature eutectics showed modification capable of producing substantial improvements in properties. The microstructures were altered and mechanical properties improved by: a.) dispersing a subordinate phase more uniformly throughout the matrix; b) replacing large continuous -network or platelike constituents with small equiaxed discontinuous phases; and c) by forming new, finely divided phases. tHE term "modification" is most commonly used to describe the refinement in microstructure of the Al-Si eutectic that occurs as a result of rapid cooling from the melt or on slow cooling after treatment with small amounts of sodium.1 "Modification" has also been used to describe the change from flake to spheroidal graphite in the austenite-graphite eutectic of cast iron.2 This change of graphite shape is accomplished by small additions of cerium or magnesium.3 Other systems have also been shown to be capable of modification, for example: Pb-Sn by copper;4 Al-Cu by sodium;5 Al-Mn by sodium;5 and Pb-Sb by aluminum.5 Although modification of Al-Si alloys and cast irons is usually accompanied by improved mechanical properties, a general definition of modification has been suggested to include the effect of small quantities of impurity elements on the microstructures of all eutectic alloys, regardless of the effect on the mechanical properties.6 In this paper, the term "modification" is employed in a broad sense to include the formation of third phases or even the supplanting of one of the binary eutectic phases by a third phase. The mechanism of modification, as for any solidification phenomenon, must be considered primarily in terms of nucleation and growth. Although both nuclea-tion and growth mechanisms are required to explain all the phenomena observed in connection with the solidification of modified eutectics, various investigators have usually favored one or the other.7"16 It has been shown that modification of a binary eutectic can be effected by addition of a solute element that has greatly different distribution coefficients or k values in the two phases of the eutectic. Under these conditions, differences in the temperatures at the solid-liquid interfaces of the two phases retard the growth of one phase with respect to the other.4 It has also been shown that increased undercooling favors a transition from a rodlike eutectic to a globular eutectic.17 A mechanism proposed for the transition from lamellar to rodlike eutectics depends on the concept of constitutional super cooling.18 The modification of eutectic alloys may be of interest for high-temperature service as well as at room temperature. Although "high-temperature eutectic alloys" may appear to be a contradiction in terms, many eutectic systems, including those studied in this work, have melting points in excess of 2400°F. One of the mechanisms by which high-temperature alloys are strengthened is dispersion of a relatively brittle phase such as an oxide, carbide, or an inter-metallic compound throughout a ductile matrix. For a given volume fraction of dispersed phase, strength is increased by decreasing the size and spacing of the dispersed particles.19'20 Furthermore, room-temperature ductility may also be increased by changing the shape of a brittle dispersed phase from platelike to equiaxed or spheroidal.8 Overaging and redissolving of the secondary phase limit the maximum temperature to which precipitation-hardened alloys can be used. However, in a binary eutectic system, both phases coexist up to the melting point. Although all eutectic structures are not completely stable,21 a dispersion-hardened cast high-temperature alloy might result if a fine distribution of one of the eutectic phases could be obtained during solidification. An additional reason for interest in eutectic alloys is their excellent castability.22 Since eutectic alloys, like pure metals, freeze at a single temperature rather than over a range of temperatures, their castability is superior to solid-solution alloys with long liquidus to solidus ranges. The purpose of this research was to study the effects of small solute additions on the microstructure and mechanical properties of a number of high-melting-point eutectic compositions.

Jan 1, 1967

By M. Vallée

This case study compares the actual production figures for the No. I and No. 2 copper orebodies of the Société Miniére Louvem, Val d'Or, Quebec, with the preproduction estimates and a postmortem geostatistical estimation using kriging techniques. The deposits considered are small subvertical sulphide orebodies which were mined from August 1970 to April 1973, producing 648,000 tons at 2.04% Cu versus the 1968 computed reserves of 671,000 tons at 2.51% Cu (with 20% dilution), thus showing a 25% overestimation of the copper contained. The postmortem geostatistical estimation based on the same 44 D.D.H. intersections available in 1968, shows 2.24% Cu (no dilution), compared to 3.23% Cu (no dilution) given by the conventional section method. Block by block kriging techniques were used, but within the ore contours as determined by the geologist. In this case, Characterized like many sulphide deposits by highly dispersed sample values, geostatistical kriging techniques permit a more realistic estimation of the metal contained within a given volume, than the conventional methods which overestimate it. This study has been conducted by the Mineral Exploration Research institute (IREM-MERI) for SOQUEM, and is one of the few case studies released with all pertinent data. More postmortem of this kind are required for geologists and geostatisticians to improve their methods and their "batting average".

Jan 1, 1977

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969