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By Henry F. Cooper, Scott E. Blouin

Large jacking test procedures that have been applied to obtain static in-situ rock properties (Ref. 1) have shown that the in-situ rock modulus and strength can be considerably less than what would be obtained from laboratory tests on intact samples. This trend is also expected to be true for dynamic properties, but few dynamic in- situ rock property tests have been conducted. During the past several years, high explosive test procedures have been developed to simulate the airblast and direct induced ground motions (Ref. 2) produced by nuclear explosions . These test procedures load large volumes (up to 10 7 f t3) of the earth with stress levels sufficiently high to produc5 feet of particle displacement over surface areas up to l0 5 ft2. This paper discusses some of the data obtained, and the implications of these results for our understanding of the dynamic response of in-situ rock. DESCRIPTION OF TEST PROCEDURES As shown in Fig. 1, the High Explosive Simulation Technique (HEST) consists of a cavity of uniform height bounded on the sides by a soil berm, above by an overburden of uniform thickness, and below by the test bed on the earth's surface. Horizontal racks of detonating cord are placed in the cavity and detonated at one end of the test bed. This detonation produces an explosive wave that propagates across the test bed, loading the earth with an overpressure pulse that decays with time because of the compression and lifting of the overburden. Since 1964, there have been approximately 40 such tests on test bed areas ranging from a few hundred to l0 5 sq ft., simulating peak overpressure conditions between about 100 and 6000 psi and specific impulses between a few and over 100 psi-sec.

Jan 1, 1971

By Anal J. Mehta, Theodore D. Tiemann

Growing demand for steel and increasing dependence upon foreign ore makes the need for developing the technology for treatment of low-grade iron ores greater than ever before• Representative of these added interests were the studies carried on at the University of Wisconsin• These studies included among others: anionic and cationic flotation, magnetic separation, roasting followed by magnetic separation, electrostatic separation, a hydrogen reduction process,6,7 and caustic digestion• The idea of removing silica by caustic extraction is not new•-1; The principle of concentrating siliceous iron ores by this method is based on the fact that silica is soluble in sodium hydroxide solution while iron oxides are essentially insoluble• For this process to be economically feasible, it is believed that some method of recovering silica from solution as a marketable by-product, with recycling of spent liquor is necessary. Precipitation of silica with carbon dioxide will allow subsequent causticizing of the spent liquor with lime• Caustic thus produced can be recycled for digestion• A flowsheet of the envisioned process is given in [Fig• 1] The purpose of this paper is to describe results obtained from the investigation of carbon dioxide precipitation of silica from sodium silicate solutions, which could be later applied to the caustic extraction process to treat low grade siliceous iron ores, particularly taconites.15 Theoretical Considerations The soluble silicates of sodium include sodium orthosilicate (2Na2O•SiO2), sodium metasilicate (Na20•SiO2), sodium disilicate (Na1O•2SiO2), and more highly siliceous products approaching Na2O•4SiO2• These materials have been described in detail by Vail•16 Stones has reported that the extraction of silica is not significantly affected by the amount of silica in solution until the Si02/Na20 ratio exceeds that of orthosilicate (Ratio = 1/2)• However, as the Si02/Na2O ratio exceeds that of metasilicate (Ratio = 1), silica extraction is significantly impaired• The present experimental work was confined to orthosilicate and metasilicate solutions, as to be successful the envisioned commercial process for the extraction of silica from siliceous iron ores would operate in this region. The mechanism of extraction of silica from aqueous sodium silicate solutions is complex in nature. For the carbon dioxide process-18 of core and mold making in which silica is also precipitated from sodium silicate solutions by gassing with carbon dioxide, the reaction of aqueous silicates with gaseous carbon dioxide has been represented by the equations: [ ] However, these equations are very much oversimplified• It has been shown that the reaction between aqueous sodium silicates and carbon dioxide gas is ionic in nature 18 Considering this fact and the mechanism for digestion of silica in aqueous sodium hydroxide, the overall conversion of aqueous sodium silicates to solid silica may be represented in ionic form by the following equations: [ ] Silicon in the silicate ion is shown here with a coordination number of 6• This may be in doubt, but it is known that ion (SiF°)-2 exists; it seems logical that the Si (OH) e 2 ion should be equally capable of existence•

Jan 1, 1977

By M. R. Pickus

THE study of the plastic deformation and recrystallization of metals has been the subject of many investigations. In regard to the simple deformational processes, such as tension and compression, the early knowledge gained from studies of polycrystalline material has been supplemented by many significant researches on the behavior of single crystals. Unfortunately, this has not been true for more complicated deformational processes. As far back as 1927, G. I. Taylor1 wrote: It is impossible in the present state of knowledge to do more than give a possible reason why (face-centered cubic) crystals set themselves with a (110) direction in the plane of rolling, and at right angles to the direction of rolling. The explanation of why the orientation of the crystal axes round the transverse direction is what it is, must be left till the distortion of metals, and particularly single crystals of metals in the process of rolling, has been studied in greater detail. That this gap in the systematic study of deformation and recrystalliza-tion has not yet been filled was indicated by C. H. Samans,2 who wrote in 1934 that "only four investigations upon cold-rolled single crystals of any of the face-centered cubic metals have been reported in the literature." Of these four studies, only those of S. Tanaka3 and T. Sakao,4 both of whom worked with aluminum crystals, had quantitative significance. The other two, carried out by F. Wever5 and W. G. Burgers,6 were of a. qualitative nature. It is our hope that the present investigation may contribute some-thing to the knowledge necessary for a rationalization of the origin of rolling textures in terms of the known behavior of single crystals, and may add pertinent information concerning the recrystallization characteristics of deformed single crystals.

Jan 1, 1938

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By Zay Jeffries

TUNGSTEN has the highest melting point of all the known metals, namely 3350° C.; it is one of the hardest of the metals; it has the highest equiaxing or recrystallization temperature after strain hardening, of any pure metal known. It is particularly distinguished because, when composed of small equiaxed grains, it is extremely. brittle and fragile at room temperature, and when possessing a fibrous structure it maybe ductile and pliable at room temperature. The common ductile metals act in exactly the opposite manner in this respect. The present paper will include a brief note regarding the manufacture of wrought and. ductile tungsten. The metallography of wrought and ductile tungsten in the various stages of manufacture will be considered more or less in detail. The general relationships between the properties of tungsten and other metals will also be considered. A discussion will be given explaining why fibrous tungsten is ductile at room temperature, even though past experience with other metals would indicate that it should be brittle. Finally, a brief note regarding some new fundamental metallographic propositions relating to all metals will be given.

Jan 6, 1918

By R. M. Sellwood

The No. 4 I.S.F. Smelter Complex at the Avonmouth Works of Imperial Smelting Corporation (N.S.C.) Limited commenced operation at the beginning of 1968. The furnace rating is 120,000 tons zinc and 40,000 tons lead per annum. Zinc and lead concentrates are unloaded onto a 1,000 tons per hour capacity conveyor belt and automatically weighed and sampled before receipt into a 48,000 ton capacity raw material store. Distribution is by a reversible boom stacker into 16 x 3,000 ton bays and recovery is by a front end loader. Materials are fed to 16 proportioning bins for feeding via continuous weigh feeders to a 132 square metre effective updraught area sinter machine with a material flow rate of 240 tons per hour over the machine. The required quantity of output lump sinter at up to 800ºC is fed to 2 x 600 ton storage bins on the I.S.F. plant. By-product SO2 rich gas is fed to a conventional wet gas single stream acid plant rated at 600 tons per day utilizing a dry N.T.P. gas volume of 100,000 cubic metres per hour. The hot sinter and preheated coke (800ºC) are automatically neighed and charged to a 27.3m2 shaft area I.S.F. fitted with 2 x 5.5 m. wide lead splash condensers. Grade 4 zinc is tapped and transferred to the zinc refinery. Conventional type lead bullion and slag are tapped from the bottom of the furnace through a separation forehearth. The refinery consists of 6 lead and 3 cadmium columns to produce some 52,000 tons per annum of S.H.G. metal. S.H.G. metal and Grade 4 metal is cast into various shapes as required.

Jan 1, 1970

The term "timbered stope" is here meant to denote stopes in which timbering is the predominant feature of the mining method. Stopes with stull sets, as in the Hecla mine, are types of timbered stopes; these types are probably the best-known. Timbering stopes by means of square sets is not as common as formerly, as the system is not often necessary, yet there are good examples and large tonnages are being mined by the method. The square set may be utilized in ordinary overhand stopes if the orebody is suitable. At some mines, square sets have been abandoned in favor of top-slicing; and at others, the square set has superseded horizontal cut and backfilling. A drift, either in the wall or orebody, is necessary before opening the sill floor. In wide deposits, there may be a grillage of drifts and crosscuts, and at least one raise to the level above is needed in each stope for ventilation and handling timbers and filling. The square sets are filled with waste rock from the hanging wall, sorted from the ore, from development work, or from the level above. As a rule, little timber is recovered. The examples include the Butte district, Mother Lode of California, Bunker Hill & Sullivan, Hecla, and Morning mines.

Jan 1, 1925

By W. C. Roberts-Austin

The subject with which the Council of the American Institute of Mining Engineers has entrusted me is one of much interest. It has been so admirably treated in America by Prof. Carl Barus* that I should have hesitated to deal with it had not the adoption of pyrometric methods in England recently occupied much attention, especially in relation to metallurgical industries and research. I shall endeavor to show what is the present state of our knowledge of practical pyrometry by briefly tracing the history of the efforts which have been made to measure high temperatures. This paper will, therefore, be limited to the consideration of those forms of appliance which have either marked distinct stages of advance, or have remained in use with more or less modification through a considerable range of time. The earliest pyrometers were essentially thermoscopes, and although their graduation presented great difficulties, their importance as affording a means for the measurement of high temperatures has been recognized for centuries. It would be difficult to illustrate this better than by a brief record of the testimony which has from time to time been offered by those who have had to apply the heat of furnaces in research or in industry, and it is mainly for the sake of the light incidentally thrown on the progress of both that the following historical notes are offered. In the eighth century, Geber, the chemist, wrote a treatise on furnaces, and showed that he was familiar with many and varied means of applying heat; but he points to the difficulties that are met with in conducting operations at high temperatures, which he attributed to inability to measure heat, his actual words being: " sed quoniam non est res ignis, quae mensuari possit." t

Jan 1, 1894

By Charles H. Fulton

There are comparatively few accurate data on the melting-or the freezing-point temperature of metallurgical slags, or on related physical phenomena, such as fluidity near the melting-point, specific heat, latent heat, etc. With the exception of the work of H. 0. Hofman,' and some older work by R. Akerman, P. Gredt, and H. M. Howe, no information is available that is of direct interest to the metallurgist. Hofman's valuable work is the only one that refers to slags produced in the metallurgy of copper and lead. The classic work of J. H. L. Vogt,2 who views slags from the standpoint of physical mixtures (solutions in which the entities are minerals), has opened up a new field in the study of slags, and has placed the investigation of such properties as melting-temperatures, etc., on a rational basis. The recent work of A. L. Day, E. T. Allen, and W. I?. White, of the Carnegie Institution, at Washington, and of European investigators3 on certain systems of silicate minerals confirms the value of the investigation of silicate series from this standpoint, and it is my aim to apply this method to metallurgical slags, in order to gain exact data of value in metallurgy. The work recorded in the present paper is the result of an investigation of reverberatory-furnace slags made for a Western smelting company to determine exactly the influence of change in composition, within comparatively narrow limits, on the melting-point. For a general discussion concerning the mineralogical character of slags and the principles on which this investigation is based, reference should be made to other work: for the subject is too large to be stated in this paper, except very briefly in the following outline:

Jan 1, 1913

By F. T. Davis

Many contributors have added to the fund of knowledge in the basic sciences related to mineral dressing during the past year. During 1964, the French edition of the Proceedings of the VIth International Mineral Processing Congress together with discussions was printed. Also, complete Preprints of papers delivered at the VIIth IMPC were published in September1. Over a third of the papers presented at VIIth IMPC dealt with fundamentals. COMMINUTION It has been postulated by Ponceleta that flaws need not exist before a stress is applied but rather the flaws are created at the tip of a propagating crack at a stress well below the theoretical breaking stress.

Jan 2, 1965

By Bernard S. Borie

THE U-A1 binary system has been studied by Kaufmann and Gordon.' They have shown that three intermetallic compounds occur in the system: UAl², UAl², and a third compound tentatively identified as UA15. UA1³ is simple cubic, a, = 4.26A. Its unit cell contains one formula weight, and it is iso-morphous with AuCu³. UA1² is face-centered cubic, a, = 7.72A, with eight formula weights per unit cell. Rundle and Wilson have shown that it is iso-morphous with Cu²Mg.² A Debye-Scherrer pattern of the Al-rich compound indicated a more complex structure than either UA1² or UA1³. The following is a report of an investigation of the crystal structure of this compound and a determination of its stoi-chiometric formula. A melt of uranium (99.9 pct pure) and aluminum (99.9 pct pure) was prepared which contained about 25 pct U by weight. It was cooled from 950" to 650°C at a rate of 500" per hr and then taken from the furnace and air cooled. An X-ray diffraction pattern of the ingot showed only lines of aluminum and the Al-rich compound. Filings from the ingot were reacted with a solution of sodium hydroxide, producing a fine black powder, the diffraction pattern of which showed no traces of aluminum. A comparison of the Debye-Scherrer pattern of our sample with the data published by Kaufmann and Gordon1 showed that it is identical with the Al-rich phase which they reported. Single crystals were obtained by cooling the melt more slowly (about 50°C per hr). After reaction with sodium hydroxide, the crystals appeared as small black needles attached to the ingot surface. Cell Size, Space Group, and Uranium Positions A series of Weissenberg photographs for rotation about two of the crystallographic axes, taken with copper radiation filtered through nickel foil, revealed an orthorhombic cell of dimensions: a = 4.41 ± 0.02A b = 6.27 ± 0.02A c = 13.71 ± 0.03A Reflections of the type hkl were observed only if: h + k + I = 2n, of the type hkO only if: h = 2n and k = 2n, of the type h01 only if: h + 1 = 2n, and of the type Okl only if: k + 1=2n. Hence, the cell is body-centered with an 001 glide plane. The evidence for the existence of the glide plane is the observed extinction of 23 possible re- flections of the type hkO with at least one index odd. There are only two space groups consistent with these data: C"" — I2ma and D28 2h — Imma.³ he possible sets of atomic positions for these space groups are: 12ma: (0 0 0; ½ ½ ½) + 4: (a) x 0 %; x % % (b) x ¼ z; x ¾ Z 8: (c) x y z; x y z; x, ½ + y, Z x, M - y, z Imma: (0 0 0; ½ ½ ½) + 4: (a) 0 0 0; 0 ½ 0 (b) 0 0 ½; 0 ½ ½ (c) ¼ ¼ ¼; ¾ ¼ ¼ (d) ¼ ¾ ¾ ; ¾ ¾ % (e) 0 ¾ Z; 0 ¾ z 8: (f) x 0 0; x 0 0; x 1/2 0; x ½ 0 (g) ¼ Y ¼; ¾ Y ¾; ¾ y ¼; 1 y ¼ (h) 0 y z; 0; ;; 0, ½ + y, z; 0, l/2 - Y, Z (i) x 1/4 z; x ¾ z; ¼ z; x ¾ z 16: (j) xy z; x y z; x y z; x y z; x, ½ + y, Z; x,½ - y, z; x, ½ - y, z; 11 1, + y,Z Though density measurements on different samples were found to vary somewhat, they were all within the range 5.7 * 0.3 g per cu cm. If it is assumed that the unit cell contains four formula weights of UAl,, it is 6.5 g per cu cm. If there were as many as eight uranium atoms per unit cell, the

Jan 1, 1952

By H. M. Otte, A. G. Crocker

SLIP, twinning, stacking faults, and precipitates on well-defined planes in a crystal produce traces that are visible on either a polished or an etched surface. The purpose of this note is to establish the usefulness and limitations of the information obtained from such traces when determining the orientation of single crystals or grains in a polycrystal. Attention will be confined specifically to traces produced by octahedral planes in cubic crystals, though most of the remarks can be taken as more generally valid. The problem of determining the crystal orientation is completely solved in principle' and in particular for the special case under consideration.1'2 Tables are available3 in which the orientations can simply be looked up when given the two or three angles between the traces. Thus a quick and simple method is available for obtaining the orientation of a crystal from surface traces. In this note two examples will be given from recently published papers and will show the use of the method with the aid of the Tables, as well as some of the precautions that should be taken in the procedure. As part of an analysis of X-ray Kossel lines, Peters and Ogilvie 4 determined from them the crystallographic orientation of the specimen. They chose a Cu-5.10 wt pct Si alloy that had been partly transformed from the a (fee) phase to the k (hcp) phase. The latter formed as very straight platelets along the octahedral planes of the a phase, and a photograph (Fig. 7 of Ref. 4) was reproduced in the paper4 of the region for which the orientation had been determined from the Kossel lines. Apart from a very small area (about 0.15 mm diam) near the top center of the photograph, the region shown was clearly all of one orientation. Traces in four different directions were readily identified. Starting with the smallest angle and proceeding counterclockwise, the angles between the traces were measured to be 27° 43', 55° 16', 64 3 43 1, and32"26'. These add up to 1802 08 1, indicating a cumulative error of 8'. The correct values should, of course, be taken from the original glass plates, or at least from prints on distortion-free paper, so the precision of the quoted values is actually greater than their accuracy. The solutions can be looked up in the Tables3 in four ways, depending on how the angles are paired, tion for the minutes of arc is required and the solution obtained will be identical for all the four pairs if the values of the angles are not in error. In a practical situation, such as this one, there are several sources of error, so that the four solutions obtained will all be slightly different. An arithmetic average of the four solutions is mathematically incorrect, but may, in special cases, give an answer close to the correct one. A rigorous procedure for refining the orientation has been described by Mackenzie;5 he gives a least-squares method that can be applied, if necessary, to this type of problem. The orientation thus determined can be compared with the one from the Kosel lines and discrepancies larger than the experimental error assigned to nonor thogonality of the X-ray or electron beam to the specimen. Here the example will only be used to illustrate the general procedure for making a very rapid rough check. From measurements on the stereographic projection, Fig. 9 of the paper,4 we can determine that the surface normal is approximately (0.434, 0.704, 0.562). From the Tables3 we find, using 28°, 55" as a good approximation to the first pair (27°43', 55°16'), that the surface normal is (0.453, 0.678, 0.579).* These two values are within 2 deg of each

Jan 1, 1967

By G. R. Love, M. L. Picklesirner

THE use of color adds a new beauty, power, and versatility to metallography. This has been amply demonstrated in a number of public exhibits and on the walls of corporate, government, and university metallographic laboratories around the world. Indeed, in a number of cases, the color not only is of esthetic value but is scientifically essential to the competent examination of particular samples and systems. Optical strain analysis,' determination of true grain size in U-A1 alloys: phase identification in Nb-base alloys,3 analysis of transformation rates in heat-treated Nb-Zr alloys,4 measurement of solidification segregation in cast Nb-Zr alloys,' study of the intermediate phases in Nb/Sn diffusion couples,6 investigation of the oxidation kinetics at various surface orientations in single crystals,7'8 and a number of other research efforts9'10 would have been vastly more difficult without the extra clarity and distinction introduced by color—either the colors resulting from particular polarized light techniques or the interference colors obtained by oxidation. It is unfortunate that the beauty of colored micro-structures cannot be shared more widely, but the economics of publishing a technical magazine apparently prohibits color plates except under extraordinary circumstances. It is doubly unfortunate that no convenient, general method exists for communicating the information available in colored microstructures to the scientific community. True, in some instances the color changes observed are dramatic enough that direct black and white photography is adequate. In photoelastic stress analysis, several orders of interference fringes may be produced and it is frequently desirable to suppress the color effects (use monochromatic light) to simplify interpretation. On the other hand, relatively minute color variations may be readily detectable by eye, be of considerable assistance in interpreting a structure, and yet be enormously difficult to reduce to an unambiguous black and white print. In order to illustrate a possible compromise or solution to the above problems, we wish to show three black and white photographs of the same region of an Nb/Sn diffusion couple whose interpretation depends heavily upon use of color techniques. These micro-structures were obtained from a section through a rod consisting of commercial-purity niobium tubing filled with 99.995 pct Sn (melt-filled in 10"6 Torr vacuum). The composite rod, measuring 500 mm long, was bent into a hairpin shape and inserted into water-cooled copper grips in a vacuum high-temperature furnace. The rod was outgassed for 2 hr at a furnace temperature of 800°C and was further heated by self-resistance using a 2.2-kva ac power supply. The rod was raised to 1910°C over a 4+-hr period, held for 15 min, slow-cooled to 1500°C over a -hr period, and free-cooled to room temperature (all temperatures were measured with W5Re/W26Re thermocouple). Throughout the heat treatment the ambient pressure was kept below 8 x lo-' Torr. Metallographic preparation of the sample was completely conventional except that it was necessary to extend the grinding steps to remove damage in the brittle NbsSn phase introduced by sectioning. No satisfactory chemical or electrochemical etch has been found for these diffusion couples; of those which have been tried, any that attack the niobium-rich phases at all attack the tin-rich phases disastrously. However, the final polishing steps did produce a slight relief effect and this, coupled with anodizing, yielded excellent clarity in the microstructures for direct observation. The anodizing voltage was chosen to give maximum change in color per unit change in composition. In this case, indeed normally, this maximum sensitivity occurred in the blue-to-red color range. The pure niobium tube wall anodized to a relatively bright blue

Jan 1, 1967

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By Gerhard Derge, Harold Markus

The introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be dcscribed. For most of the additions, solutions containing 0.001 and 0.01 moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-l,ol~ate as follows: pH 0.1 M NaHC0............................................ 8.4 2 parts 0.1 M XaHCOr, 1 pa.rt 0.1 M NaZCO?................. 9.5 1 part 0.1 M NaHCOs, 2 parts 0.1 M iVa.,C03. ................ 10.0 0.1 M Na2C0............................................. 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves—sulphnte, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only -fuoridc, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also—phosphate, pcrborate, and chromate. Potential Measurements f The time-potential curves represntative of group 1 are shown in Fig. 1. These are the curves for 0.005 M sulphate ion and their similarity

Jan 1, 1939