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By C. H. Benedict

A 2000-ton ammonia leaching plant has been operated by the Calumet & Hecla Mining Co., at Lake Linden, Mich., continuously since February, 1917, except from April, 1921, to April, 1922, during the period of depression following the European war. A description of this plant has been published elsewhere.1 The present article describes the operation of the plant since 1917, together with the changes in the process that have been found to be advisable. In spite of the fact that this plant and that of the Kennecott Copper Co. are the only ones operating on a large scale, much experimental work is being done on ammonia leaching, as applied to oxidized ores, and it is to aid these and other investigators that this detailed account is given. For the benefit of those unfamiliar with the original article, the following short abstract is given, as an introduction to a more detailed account of the process and the reasons for present practice.

Jan 2, 1924

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s'S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.' There are a few marked discrepancies in the intensity comparison of the two s's, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s' have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955

By J. C. Bayles

Jan 1, 1886

By Henry M. Howe

Many direct processes have been proposed for the treatment of oxidized ores of copper by reducing the copper oxide to the metallic state, and by separating it from its impurities by a subsequent fusion. The radical objection common to all the methods which have come to my notice, except those in which sulphur plays the prominent part, is that the very deoxidizing agent which effects the reduction of the copper oxide, inevitably reduces at the same time a very considerable part, if not the whole, of the iron which almost invariably accompanies copper in its ores. The result is that, when the ore is subsequently fused, a very great quantity of the already reduced iron separates from the slag along with the copper, alloying with it, and necessitating costly subsequent operations for its separation. Thus, at Perm, in the Urals," the product of the fusion of ferrnginous copper oxides is a mixture of one hundred and fifty-tive parts of highly cupriferous pig iron with two hundred and fire parts of very impure and ferruginous black copper, containing Pome 10 per cent. of' carbon and iron, though free from sulphur, and of course very difficult to refine. If, in order to avoid this reduction of iron to the metallic state, the reducing action be made feebler, it inevitably results that a considerable part of the copper as well escapes deoxidation; and, consequently, the slags are so rich that it becomes necessary to treat them subsequently in order to recover the copper which they contain. Thus,. in treating native copper, at Lake Superior, where the reducing action is purposely made feeble in order to prevent the deoxidation of the iron, the slags from the first fusion of the ore carry so much copper as to render it imperative to treat them again, which is done in a cupola. And yet, in spite of so far weakening the reducing action as to cause a notable slagging of the copper, a very considerable reduction of iron actually takes place. These are the two dangers which threaten the smelter of oxidized copper ores. If he wishes to avoid slagging his copper, he must have so strong a deoxidizing action as to reduce a great deal of his

Jan 1, 1879

By H. M. Howe

(Read at. the Lake George Meeting, October, 1878.) MANY direct processes have been proposed for the treatment of oxidized ores of copper by reducing the copper oxide to the metallic state, and by separating it from its impurities by a subsequent fusion. The radical objection common to all the methods which have come to my notice, except those in which sulphur plays the prominent part, is that the very deoxidizing agent which effects the reduction of the copper oxide, inevitably reduces at the same time a very considerable part, if not the whole, of the iron which almost invariably accompanies copper in its ores. The result is that, when the ore is subsequently fused, a very great quantity of the already reduced iron separates from the slag along with the copper, alloying with it, and necessitating costly subsequent operations for its separation. Thus, at Perm, in the Urals,* the product of the fusion of ferruginous copper oxides is a mixture of one hundred and fifty-five parts of highly cupriferous pig iron with two hundred and five parts of very impure and ferruginous black copper, containing some 10 per cent. of carbon and iron, though free from sulphur, and of course very difficult to refine. If, in order to avoid this reduction of iron to the metallic state, the reducing action be made feebler, it inevitably results that a considerable part of the copper as well escapes deoxidation ; and, consequently, the slags are so rich that it becomes necessary to treat them subsequently in order to recover the copper which they contain. Thus, in treating native copper, at Lake Superior, where the reducing action is purposely made feeble in order to prevent the deoxidation of the iron, the slags from the first fusion of the ore carry so much copper as to render it imperative to treat them again, which is done in a cupola. And yet, in spite of so far weakening the reducing action as to cause a notable slagging of the copper, a very considerable reduction of iron actually takes place. These are the two dangers which threaten the smelter of oxidized copper ores. If he wishes to avoid slagging his copper, he must have so strong a deoxidizing action as to reduce a great deal of his * Rivot, Prineipes Généraux du Traitement des Minerais Métalliques, i, p. 79.

Jan 1, 1879

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By Y. A. Topkaya

The placer gold occurrences at Sart Çayl, Manisa, Turkey, the legendary River Pactolus of King Croessus, were evaluated in this study to determine if this deposit contains sufficient recoverable value to justify development and exploitation. The gold occurs both in the upper Neogene conglomerates and the alluvium derived from these conglomerates. The total reserve in the whole region is estimated to be 500 million cubic metres. Samples were taken of the upper conglomerate and in the alluvium in an attempt to determine the amount and the physical nature of the gold. The gold in samples was recovered by screening out barren oversize followed by washing the sand and gravel through riffled sluices. The resulting sluice concentrate was later panned and amalgamated at site. Laboratory cyanidation testing of some samples for control purposes was also done. The average calculated free gold was found to be about 90-100mg/m3 and the size of gold flakes found was quite small. The field as well as laboratory testing of the samples of Sart Çay1 indicated that the potential reserves in this region could only be developed as a sand and gravel operation and the gold could be recovered together with the heavy minerals as a byproduct.

Jan 1, 1984

By Clarence W. Balke

SMALL buttons of fused tantalum have been produced by arc fusion in a vacuum, by drawing an arc between sticks of pressed tantalum and a tantalum-faced water-cooled copper block. However, ingots of appreciable size can be produced only by the heat-treatment of bars pressed from powder. The following outline covering the production of finished bars of tantalum by the methods of powder metallurgy is also used for the production of columbium, taking into account the difference in the melting points of these two metals. PRESSING THE POWDER With possibly a few exceptions, a pressing operation is one of the essential steps in the practice of powder metallurgy. In fact, the author's experience with a number of high-melting-point metals and with numerous types of hard carbide compositions has led him to believe that this operation is often one of the most important in the entire process, and frequently one of the most difficult to carry out in a satisfactory manner. Defects due to improper pressing can readily lead to a defective finished product. It is the author's opinion that rarely is a bar or other article pressed from metal powder in such a way that all parts of the piece are uniformly pressed. The nearest approach to uniformity of pressing is possibly attained when the powder is contained in a flexible receptacle, such as rubber, and is pressed under a liquid by hydrostatic pressure. However, this method is not generally applicable. Hydraulic pressing in steel dies where one or two punches are forced into the die must usually be resorted to. As the pressure in such a die is built up, the powder begins to cling to the walls of the die with a tenacity dependent upon the nature of the powder, and this results in a bridging action, so that the layers of powder adjacent to the moving punch are pressed more heavily than those further removed in the mass. Frequently, as the pressure is carried higher, there may be a mass slippage of the powder upon itself, with the result that slip cracks are formed within the pressed

Jan 1, 1938

By B. Post, D. Moskowitz, F. W. Glaser

Lattice parameters of various hafnium compounds, two borides, a carbide and a nitride were determined. Some physical properties were measured and comparisons with the properties of the corre-sponing zirconium compounds were drawn. A LTHOUGH borides of transition metals have A been extensively investigated in recent years, there are few references in the literature to borides of hafnium. This is not surprising, in view of the extreme scarcity and great cost of the purified metal. Becker' reported the existence of a boride, carbide, and nitride of hafnium; he listed the formulas as HfB, HfC, and HfN. However, in his work no mention was made of chemical analyses of the reaction products. In this paper results of a study of various hafnium compounds, including borides, carbides, and nitrides, are reported. It was expected, of course, that these compounds would closely resemble their zirconium analogues, which have previously been extensively investigated. Three borides of zirconium are known: ZrB,² ZrB,² and ZrB212.4 In addition, one carbide, ZrC,5 and one nitride, ZrN,5 have been reported. It should be noted that ZrB and ZrB12 are stable phases only in relatively high-temperature regions, unlike ZrB2, which is stable from room temperature to its melting point." It was felt that hafnium would yield corresponding borides, carbides, and nitrides with similar stability ranges. Experimental Procedures and Results A quantity of hafnium metal that was better than 97 pct pure, with zirconium as its major impurity, was furnished by the Argonne National Laboratories. The boron powder used was approximately 96.5 pct pure. In general, the procedure involved mixing the metal and boron powders in the desired proportions, and subsequently hot pressing them. The resulting specimens were analyzed chemically and phases present were identified by X-ray diffraction methods. A Philips Norelco Geiger counter spectrometer was used for identification of components and for measurement of lattice constants. Filtered copper radiation was used for all X-ray work. Electrical resistivity and density measurements were carried out at room temperature. The stable diboride, HfB2, will be described first. Stoichiometric quantities of boron and metal were heated to approximately 2000°C during hot pressing. The reaction product was shown by X-ray diffraction methods to be isomorphous with ZrB2 (space group Dlgh; P6/mm). Values of lattice constants of HfB2 compared with those of ZrB2 are shown in Table I. The calculated density of HfB2 is 11.2 g per cc, compared with a measured (pycnometric) value of 10.5 g per cc. HfB2 specimens prepared under a wide variety of conditions (including variations in initial Hf-B ratios) showed only insignificant variations in lattice constants, indicating a very narrow range of homogeneity. Like ZrB2,7 HfB2 is an excellent electrical conductor. The resistivity at room temperature of hot-pressed samples, approximately 85 pct dense, is 12 microhm-cm. This compares favorably with the electrical resistivity of 10 mi-

Jan 1, 1954

By H. T. Mulryan

For the producer of industrial rocks and minerals, marketing is often the only means of survival. His material must be sold. There is little of the impersonal force of the market regulating supply and demand. No commodity exchanges facilitate his efforts to dispose of the material he produces, and the success or failure of his business depends primarily on prompt and correct response to market needs and requirements. This response is particularly vital where materials of low unit value must be shipped to distant consumers owing to a relative rarity of suitable deposits. The advantage of positive response to change can best be illustrated by hypothetical cases showing how problems can be turned into opportunity through marketing ingenuity. Three such cases dealing with materials of unit values in the range of $5 to $100 per ton are outlined below.

Jan 7, 1969

Jan 1, 1957

By F. C. Miller

The metallurgical fuel of Colorado, Utah, and New Mexico has been a Veiny tardy member in the caravan of western industrial progress. The history of western coke has naturally been closely related to the development of the metallurgy of iron and steel and the precious metals, in the State of Colorado. It was at Leadville, with a population of 300 in 1877, that the Sentinel was published by Richard S. Allen. The Sentinel gave very full accounts of the various mineral discoveries at the new town of Leadville, which found their way to the more widely circulated journals of the East, and attracted the attention of many people. At the close of 1878, a census slowed a total of 5040 persons. The first smelter was established in 1877, at Malta, two miles from Leadville, by A. R. Meyer, but was not successful. It was succeeded by the Harrison Reduction Works, in 1878. The La Plata began with one furnace in June, 1878, and in 1879 had four furnaces in active operation. These furnaces used charcoal for fuel, and, because of hot tops, suffered a tremendous loss in lead and silver. This difficulty was overcome by the erection of 50 single-bank 10-ft. beehive ovens at Crested Butte, Colo., in 1880. The slack coal sent to these ovens was very pure, and yielded a coke carrying as little as 4.5 per cent. ash. Among the pioneers in the Leadville district were Grant, Eddy, James, Billings, Eiler, and Dickson. To these men the West owes the present expansion of its mining industry, and the erection of metallurgical processes for the treatment of precious metals. On Mar. 1, 1876, Pueblo was connected to the Atchison, Topeka & Sank Fe by the Pueblo & Arkansas Valley branch. The first smelter was erected in Pueblo by Mather and Geist. This modest plant grew into the immense Pueblo Smelting and Refining Co., now a part of the American Smelting and Refining Co. Coke for these small furnaces was made from unwashed Engleville coal, in 186 single-bank 12-ft. ovens at El Moro, in the Trinidad district, and it was not uncommon for the percentage of ash to exceed the percentage of fixed carbon in the coke. On Jan. 23, 1880, the Colorado Improvement Co. consolidated

Jan 1, 1920

By Samuel S. Wyer

The following description of methods for conducting gas-producer tests is probably the first attempt to give the subject an analytical, thorough and comprehensive treatment. In some cases where tests have been made, the methods have been so unsystematic and ambiguous that it has been impossible to secure comparable results. To eliminate this difficulty, the following provisional code of gas-producer tests— which has some resemblance to the code of boiler-trials of the American Society of MechanicalEngineers—has been developed. The primary object in testing a gas-producer is to determine whether the producer is working satisfactorily or, what is the same thing, to see if the efficiency is as high as it should be with the type of producer in question; and also to find out if the composition of the resulting gas is adapted to the work it has to do. In order that the test shall be of any value, it must be thorough and comprehensive, and must be conducted with skill and care. When so conducted, the test will reveal the economy of the'producer; and, by making suitable changes, the efficiency will often be increased very much. As a result of the tests made by Jenkins,' the efficiency was raised from 56.2

Jan 1, 1906

By R. A. Breitrick, J. N. Swinderman, J. J. Cooper, H. L. Bauer Jr.

The Robinson Mining District, near Ely, Nev., is one of the major porphyry copper districts in the world. Within the district is an eight mile long east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize some of the relations between porphyry alteration, metamor-phism, and mineralization: 1) Disseminated copper ore does not occur in unaltered porphyry or in m-metamorphosed sedimentary rocks. 2) Sedimentary rocks have been only weakly metamorphosed where intruded by unaltered porphyry. 3) Intensely metamorphosed sedimentary rocks are found only adjacent to altered porphyry. 4) Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5) Disseminated ore is found in altered porphyry and adjacent metamorphosed sedimentary rocks. 6) In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7) Chemical changes in the altered porphyry and metamorphosed rocks appear to be related. The foregoing relations support a hypothesis that the porphyry alteration, the metamorphism of the sedimentary rocks, and the ore deposition were all part of a continuous hydrothermal process which probably closely attended the porphyry intrusion. The Robinson Mining District, most often referred to as the Ruth or Ely District, is located in eastern Nev. and is one of the major porphyry copper districts of the world. Production from 1908 through 1962 was nearly 250 million tons of ore averaging a little over one percent copper with a total metal value of nearly one billion dollars. The ore has been produced from six major disseminated-type deposits with the Liberty Pit deposit accounting for 70% of the total district production. Less than one million tons of base metal and gold ores have been produced from the replacement-type deposits of the district. Approximately 20% of the district production has come from underground mining operations; the pit ore has been mined with shovels and removed by train haulage, truck-train haulage combinations, truck haulage, and presently by a combination truck-skip system. Many of the ore deposits formerly worked by underground methods have been and are being exploited by open pit methods. (See Fig. I.) Two co.'s have accounted for virtually the entire production from the district. In 1958 Kennecott Copper Corp. acquired the district assets of Consolidated Coppermines Corp. and is now the sole ore producer in the district. Present operations are confined to the Liberty Pit where 22,500 tons of ore averaging a little less than 0.8% copper is mined per day. Cutoff grade is 0.4% copper, and the stripping ratio is three to one. The ore is hauled by rail 23 miles to the McGill Reduction Plant where it is concentrated to about 20% copper. Molybdenite is recovered as a by-product in the mill. The copper concentrates are smelted in McGill, and the blister copper is shipped for refining to Balt. where gold, silver, platinum and palladium are recovered. The Robinson Mining District has been well known as a porphyry copper district for the past fifty years, but many geologists are unaware of the fact that a large portion of the production has come from disseminated ore found in metamorphosed sedimentary rocks. The scope of this paper describes the occurrences of disseminated ore in the various metamorphosed sedimentary rocks, and presents evidence for the hypothesis that these ores are genetically, spacially, and coevally related to the disseminated ore in the porphyry rocks. Publication of this paper was granted by the management of Kennecott Copper Corp. A. H. James suggested and encouraged the writing of the manuscript. Special mineralogical and spectrographic analyses were performed by the Kennecott Research Center. The deposits of the district have been studied by many geologists since the turn of the century, and

Jan 1, 1964

By G. A. Chadwick, D. Jaffrey

The morpho1ogies and orientation relationships of the phases in the Sn-Zn and A1-A13Ni eutectic systems were examined by electron microscopy and X-ray diffraction techniques. In each alloy the "transition" from the lamellar to the fibrous morphology was found to be one of scale, not of type. The minor phase in both systems exhibited certain well developed facets which were not affected by changes in the ingot solidification rate. The crystallographic relationships displayed by the pairs of phases in both systems were also insensitive to the growth rate. In the Sn-Zn alloy, the unique relationship of: growth direction - II [1201 Sn - II [01101 Zn and ribbon interface plane 11 (101) Sn 11 (7012) Zn was determined. The Al-Al3Ni alloy phases did not possess any particular orientation relationship, though the Al3Ni phase invariably grew in the [010] direction and exhibited the same set of facet planes. These results are discussed in relation to current eutectic growth theories and explanations of the "lamellar to fibrous transition". THE lamellar to fibrous transition that occurs in many eutectic alloys has been the subject of considerable speculation and experimental study. In some alloys it can be induced solely by an increase in the solidification rate,'-3 whereas in others the transition supposedly occurs only if the lamellae are forced to grow out of the overall ingot growth direction.4-6 he cause of this latter type of transition has been attributed to deviations of the lamellae from their low energy habit planes;4'5'7 fibers are produced because the sustaining force for lamellar growth (a low energy boundary) is destroyed. Implicit in these explanations is the assumption that fibers are circular in cross-section and completely lacking in low energy inter-phase interfaces. The "natural" growth rate dependent transition has been studied less thoroughly although Tiller8 has attempted a theoretical explanation of it. Tiller's arguments are not completely satisfactory9 but his suggestion that the relative undercoolings of the solid/liquid interface for lamellar and fibrous morphologies are growth rate dependent cannot be totally discounted; it is possible, for instance, that the relative interfacial undercoolings could alter and produce the observed morphology change if the orientation relationships between the phases and the associated interphase bound- ary energies were sensitive to growth rate. Salkind et al." have reported finding a change in the orientation relationships in the A1-A13Ni system accompanying the lamellar to fibrous transition, but contradictory evidence has also been reported for this3'" and another system,12 so the position remains unclear. In an attempt to clarify matters a study was made of the "lamellar to fibrous" transition in the Sn-Zn and A1-A13Ni eutectic systems; the morphologies of these two selected systems are quite similar when viewed by optical microscopy. In the present research the morphologies and morphology changes were investigated by electron microscopy. The orientation relationships existing between the eutectic phases were also determined for both morphologies in both eutectic systems. EXPERIMENTAL PROCEDURE The materials and method of alloy preparation and ingot solidification for the Sn-Zn system have been reported previously.2 In this investigation nine horizontally grown ingots of the highest purity (99.9997 pct) were used. The temperature gradient in the melt was not intentionally varied and was approximately 10°C per cm. Seven growth rates between 1.3 cm per hr and 20 cm per hr were imposed. The A1-A13Ni alloys were prepared from "Spec. Pure" nickel and 99.995 pct aluminum by melting the components in an open alumina crucible and casting the melt into the cold graphite mold. Six ingots of the Al-Al3Ni alloy were unidirectionally solidified at growth rates from 1 cm per hr to 12 cm per hr under high purity argon. A typical ingot was 20 cm long, 1 cm wide, and 0.75 cm to 1.5 cm thick. Samples taken from the bars at positions 12 cm from the nucleation end were examined by conventional orthogonal-section metallo-graphic techniques. When required, samples were mounted for X-ray diffraction analysis using the Laue back-reflection technique with a finely focussed X-ray source. The surfaces of the A1-A13Ni specimens were prepared by mechanically polishing them down to the 1 µ diamond pad stage followed by an electropolish in 80/20 methanol/perchloric acid solution at 0°C and 20 to 30 v. The Sn-Zn specimens were repeatedly polished on an alumina pad and etched in hot dilute (2 pct) nitric acid until the diffraction spots were found to be sharp. Thin films of the alloys were prepared for observation in an electron microscope by spark machining thin discs (0.03 to 0.04 in. thick) from longitudinal and lateral sections of the bars and elec-trolytically thinning them via a jet polishing technique. For the A1-A13Ni eutectic alloy, an 80/20 mixture of ethanol/perchloric acid at 40 v and 20°C was found to be satisfactory. A solution of 70/20/10 methanol/perchloric acid/butylcellosolve at 25 v and 20°C was used on the Sn-Zn alloy. For the former alloy the jet nozzles (cathodes) and the disc clamps were of aluminum;

Jan 1, 1970

By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes' expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers' mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

By Holbrook G. Botset

Experiments performed in this laboratory on the flow of gas-liquid mixtures through unconsolidated sands have been described and discussed in an earlier paper.4 In these earlier experiments a definite relationship was found between the liquid saturation of a sand and its permeability to the liquid or gas phase. Furthermore, the nature of the sand, the permeabilities of the sands over a range between 17 and 260 darcies, appeared to have a negligible effect upon the saturation-permeability relation. Likewise experiments indicated that the viscosity of the liquid, or the substitution of an immiscible liquid for the gas phase, had only a very slight effect on the permeability-saturation relation. This conclusion has since been definitely confirmed by the experiments of M. C. Leverett3 on the flow of oil and water through unconsolidated sands. The sands used by Leverett were of very low permeability (between 6.8 and 1.04 darcies), while the oil-water viscosity ratio varied between 90 and 0.057. Since the sands that constitute petroleum reservoirs are largely consolidated, although of widely varying degrees of consolidation, it was desirable to extend the experiments on gas-liquid mixtures to consolidated sand. In the study of consolidated sands additional variables are involved, but for the initial experiments the only new variable to be introduced was the cementing material. Experimental Procedure A comparatively limited assortment of sandstones was available for the selection of the experimental material. Of these, the Nichols buff sandstone appeared to be most suitable. It gives no visual evidence of any bedding planes, it has a firm structure, permitting easy handling, and its permeability is about 0.5 darcy. Its only disadvantage is the fact that it contains an appreciable amount of ferric oxide which, for experiments involving water, will hydrate and reduce the permeability. This

Jan 1, 1940

By Holbrook G. Botset

Experiments performed in this laboratory on the flow of gas-liquid mixtures through unconsolidated sands have been described and discussed in an earlier paper.4 In these earlier experiments a definite relationship was found between the liquid saturation of a sand and its permeability to the liquid or gas phase. Furthermore, the nature of the sand, the permeabilities of the sands over a range between 17 and 260 darcies, appeared to have a negligible effect upon the saturation-permeability relation. Likewise experiments indicated that the viscosity of the liquid, or the substitution of an immiscible liquid for the gas phase, had only a very slight effect on the permeability-saturation relation. This conclusion has since been definitely confirmed by the experiments of M. C. Leverett3 on the flow of oil and water through unconsolidated sands. The sands used by Leverett were of very low permeability (between 6.8 and 1.04 darcies), while the oil-water viscosity ratio varied between 90 and 0.057. Since the sands that constitute petroleum reservoirs are largely consolidated, although of widely varying degrees of consolidation, it was desirable to extend the experiments on gas-liquid mixtures to consolidated sand. In the study of consolidated sands additional variables are involved, but for the initial experiments the only new variable to be introduced was the cementing material. Experimental Procedure A comparatively limited assortment of sandstones was available for the selection of the experimental material. Of these, the Nichols buff sandstone appeared to be most suitable. It gives no visual evidence of any bedding planes, it has a firm structure, permitting easy handling, and its permeability is about 0.5 darcy. Its only disadvantage is the fact that it contains an appreciable amount of ferric oxide which, for experiments involving water, will hydrate and reduce the permeability. This

Jan 1, 1940

By I. R. Kramer

Studies of the effect of size of the specimen on the change of slopes of Stages I and 11 by surface removal showed that the change of Stage I was independent of size with respect to the polishing rate; however, the change in the slope of Stage 11 with polishing rate increased directly in proportion to the surface area. The removal of the surface during the test affected the plastic deformation characteristics of gold, aluminum, and zinc single crystals and polycrystalline aluminum. The apparent activation energy of aluminum was found to be decreased markedly by removing the surface during the deformation process. In previous papers1-3 it was shown that the surface played an important role in the plastic deformation of metals. By removing the surface layers of a crystal of aluminum by electrolytic polishing during tensile deformation, it was found that the slopes of Stages I, II, and III were decreased and the extents of Stages I and II were increased when the rate of metal removal was increased. By removing a sufficient amount of the surface layer after a specimen had been deformed into the Stage I region, upon reloading, the flow stress was the same as the original critical resolved shear stress and the extent of Stage I was the same as if the specimen had not been deformed previously. The slope of Stage I was decreased 50 pct and that of Stage 11 decreased 25 pct when the rate of metal removal was 50 X 10"5 ipm. These data show that in Stage I the work hardening is controlled almost entirely by the surface conditions, while in Stages 11 and III both surface conditions and internal obstacles to dislocation motion are important. It appears that during the egress of dislocations from the crystal, a fraction of them becomes stuck or trapped in the surface regions and a layer of a high dislocation concentration is formed. This layer would not only impede the motion of dislocations, but would provide a barrier against which dislocations may pile up. In this case, there will be a stress, opposite to that of the applied stress, imposed on the dislocation source and dislocations moving in the region beyond this layer. It has been found convenient to refer to this layer as a "debris" layer. The "debris" layer may be similar to the dislocation tangle observed by thin-film electron microscope techniques.4 Reported in this paper are the results of studies on the effects of removing the surface during plastic deformation on aluminum crystals of various sizes. The effects of the surface on the yield point behavior of gold and high-purity aluminum crystals as well as the creep behavior were also determined. The effects of surface removal on polycrystalline aluminum (1100-0 and 7075-T6) are also reported. EXPERIMENTAL PROCEDURE For those portions of the investigation involving creep and tensile specimens, single crystals, having a 3-in. gage length and a nominal 1/8-in. sq cross section, were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The single crystals were prepared from materials which had initial purities of 99.997, 99.999, 99.999, and 99.999 pct for Al, Cu, Zn, and Au, respectively. The aluminum specimens for the size effect studies were prepared through the use of a three-tier mold in which crystals having a cross section of 1/8, 1/4, and 1/2 in. were grown from a common seed. The mold design was arranged so that one 1/2-in. crystal, two 1/4-in. crystals, and four 1/8-in, crystals of the same orientation could be cast. With this technique, it was possible to obtain only one set of crystals with the same orientation. Because of this limitation, it was not possible to determine both the changes of extent and slope of the various stages since a large number of crystals of the same orientation would have been required. Instead, only the change of slope as a function of the rate of metal removal was studied by abruptly altering the current density of the electrolytic polishing bath at various strains within the regions of Stages I and 11. The experimental techniques used for the tensile studies were essentially the same as those used previously.1,3 The specimens were deformed in a 200-lb Instron tensile machine, usually at a rate of 10-5 sec-5. A methyl alcohol-nitric acid solution was used as the polishing bath for aluminum. The temperature was maintained constant within ±0.l°C by means of a water bath. The tensile machine was

Jan 1, 1963

The co-operation of the members of the Institute is earnestly sought by the Committee on Nominations, recently appointed by the Board of Directors, in its work of formulating a ticket for officers and places falling vacant in the Board of Directors in February, 1916. The Committee must present the official ticket of nominations to the Board of Directors at its October meeting. Members are, therefore, urged to send promptly their nominations for officers and Directors in order that the Committee may have an opportunity to give them full consideration. The officers to be elected at the annual meeting in February, 1916, are: One officer, known as Director and President. Two officers, known as Director and Vice-President. Five officers, known as Director. The officers of the Institute whose terms expire are as follows: President, William L. Saunders (not eligible for re-election). Past President, Charles F. Rand. Vice-Presidents, Thomas H. Leggett, District 0; Fred W. Denton, District 4.

Jan 9, 1915