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By J. B. Mackintosh

The quantitative determination of copper, by means of electrodeposition, offers so many advantages, that it is to he preferred, when properly executed, to 611 other methods for ease and accuracy. The object of the present paper is to give the results of a number of experiments made during the past few months, and to indicate some sources of error, which must be avoided in order to attain the necessary accuracy. In 1867, C. Luckow, in competition for a prize offered by the directors of the Mansfield Copper Works, submitted the following

Jan 1, 1882

By R. M. Treco

THE purpose of this work has been to investigate recrystallization characteristics of zirconium after cold working and annealing. In order to do this, hafnium-contain ing crystal bars of Foote Mineral Co. iodide zirconium were selected for high purity. maximum diameter (about ½ in.), brightness of surface, and absence of core wire. A typical lot analysis is shown in Table I. In order to obtain uniformity of starting material, all bars were cold-swaged to 0.310 in. diam, annealed for 2 hr at 1000°C, and furnace cooled.

Jan 1, 1957

By Irwin Roman

PART I. INTRODUCTION THE literature of geophysics as applied to the discovery of mineral deposits has been very extensive during the past few years, but there seem to be few references to the use of the method of least squares for obtaining better interpretations of the observed data .2 There seems to be a general reluctance among geologists and. engineers to acquire the technique of least squares, in spite of the fact that a thorough knowledge of the theory is not necessary for the use of the method.

Jan 1, 1931

By Earle E. Schumacher, W. C. Ellis, John F. Eckel

Copper-calcium alloys are of interest as materials for use in deoxidized conductors of high conductivity. That calcium is effective in deoxidizing and degasifying copper is well known. Brandenberg and Wiensl have described the use of calcium in the casting of sound copper and state that the deoxidation can be carried out without difficulty. The castings that they prepared were sound and sufficiently ductile to permit wire drawing. Pratt,2 in British Patent No. 1699 (1907), has claimed the use of calcium for the deoxidation and degasification of copper. Masing3

Jan 1, 1930

By Earle Schumacher

COPPER-CALCIUM alloys are of interest as materials for use in deoxidized conductors of high conductivity. That calcium is effective in deoxidizing and degasifying copper is well known. Brandenberg and Wiens1 have described the use of calcium in the casting of sound copper and state that the deoxidation can be carried out without difficulty. The castings that they prepared were sound and sufficiently ductile to permit wire drawing. Pratt,2 in British Patent No. 1699 (1907), has claimed the use of calcium for the deoxidation and degasification of copper. Masing3

Jan 1, 1929

By Stephen Royce

[PAGE Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine (TP 2000 by JOHN W. VANDERWILT, Min. Tech., May 1946. Discussion by STEPHEN ROYCE and the Studies of the Design of Shaped Explosive Charges and Their Effect in Breaking Concrete Blocks (TP 2157 by GEORGE B. CLARK, Min. Tech. May 1947. Discussion by PHILIP B. BUCKY, V. H. CLARK, E. D. GARDNER, M. H. HAWKINS, H. L. WALKER, and the author) 2 See TP 2377, Min. Tech., May 1948 for discussion of San Manuel ProsPect (TP 2255 by H. J. STEELE and G. R. RUBLY, Min. Tech., Sept. 1947. Discussion by L. KENNETH WILSON, ELDRED D. WILSON and the authors)] Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine STEPHEN ROYCE•-It is interesting to note from B, Fig 2, how closely the subsidence limits approximate to the 60° angle of draw, which is so commonly found to rule in large scale rock subsidence. The tension cracks shown at B are commonly found in the initial stages of subsidence movement and spread like a halo about subsidence limits as movement extends. These tension cracks usually grow into escarpments later on. Apparently from the illustrations and description given, a system of vertical fractures is the predominating weakness in the wall rock at Climax, and therefore both tension cracks and escarpments are prevailingly vertical in attitude. The illustrations in Mr. Vanderwilt's article seem to conform to the general rule that yield by subsidence is heralded by tension cracks which foreshadow the appearance of the subsidence scarps which are both described in the paper and shown in Fig 2. The difference between the B side and the A side of Fig 2 is apparently caused mainly by the vertical fracturing which controls subsidence at Climax as compared to the relatively homogeneous rock formation at A upon which the original figure in Peele's Handbook was based. The draw at B is exactly 60°, while the draw at A is a little flatter. The influence of the vertical fractures explains the difference. The surprising feature is the relatively small deviation from the general 60° draw line, which is about the average of rock subsidence experience. The influence of local fracture systems, faults and bedding in controlling subsidence all the way from extremely low angles of draw to vertical is rather fully discussed in the Peele's Handbook article referred to. The more illustrations of subsidence there are published the better will be our knowledge. The general principles are pretty well established. The wide local differences reflect the effect of local conditions. This paper is a very valuable contribution to the subject, and for the benefit of the mining industry, it is to be hoped that there will be many more such clear and concise presentations. Particularly block caving is apt to be of greatly increasing importance in the future of a mining industry that must meet high labor costs. More examples of block caving from small scale to large scale operations like those at Climax will serve a vital need. JOHN W. VANDERWILT (author's reply)-I would like to thank Mr. Royce for his discussion; however, in his comments the meaning of subsidence, draw and tension cracks is not entirely clear. As used in my discussion of subsidence at Climax, subsidence refers to movements involving appreciable downward displacement. Tension cracks indicate only

Jan 1, 1947

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By M. F. Goudge, R. V. Tomkins

Sodium sulfate is an important chemical raw material that is being used in ever increasing quantities in modem industry. It comes on the market mainly in three forms: (1) Salt cake (Na2SO4), a relatively crude form of the anhydrous salt containing up to 3 pct impurities, and comprising about three-quarters of the North American production; (2) anhydrous sodium sulfate (Na2SO4), a refined form containing less than 0.3 pct impurities; (3) Glauber's salt, the decahydrate (Na2SO4.10H2O) containing 55.9 pct water of crystallization. Competing with salt cake from natural sources is byproduct salt cake from a number of industrial operations. For instance there is Mannheim cake resulting from the manufacture of hydrochloric acid by the reaction of salt (NaCl) and sulfuric acid in Mannheim furnaces; rayon cake, a high-quality product, resulting from the process of making rayon by the viscose process; chrome cake from the processing of sodium chromate to dichromate; phenol cake from the manufacture of phenol; also byproduct sodium sulfate resulting from the conversion of lithium sulfate to lithium carbonate; from the processing of sodium tetraborate to boric acid; from converting sodium formate to formic acid; and in the manufacture of cellophane. Sodium sulfate is also obtained as a byproduct in the manufacture of isosebasic acid. In addition strong competition has resulted from imports of byproduct salt cake from the chemical industries of a number of highly industrialized European countries. However in recent years due to technological changes the output of byproduct salt cake is rapidly diminishing and the natural deposits are becoming the most important source of sodium sulfate used in North America. For instance, the production of hydrochloric acid in Mannheim plants has become obsolete and thus the greatest single source of byproduct salt cake will disappear. Also viscose rayon is meeting strong competition from nylon and other synthetic fibers and production of byproduct salt cake from this source may do little more than remain at the present level. These factors together with increasing demand for sodium sulfate point to increased production from natural sources. In 1958, 36 pct of the total United States production was derived from natural sources and in addition 97,000 short tons was imported so that over 40 pct of the total consumption was supplied by natural sources whereas in 1953 the proportion was only 24 pct. The rapid growth in production is shown in Table 1. Principal Sodium Sulfate Minerals There are many minerals in which sodium sulfate is a constituent but those of commercial importance at the present time, and consisting wholly of sodium sulfate in either the hydrous or anhydrous states, are mirabilite and thenardite. Minerals of potential importance but consisting in part of compounds other than sodium sulfate are glauberite in which sodium sulfate is combined with calcium sulfate, and blödite in which sodium sulfate is combined with magnesium sulfate. Mirabilite (Na2SO4.10H2O) the decahydrate, consists of 24.8 pct SO3, 19.3 pct Na2O, and 55.9 pct H20. It is a colorless to opaque, soft, water-soluble mineral with a slightly bitter taste. It has a hardness of less than 2 and a specific gravity of 1.48. It forms long needle-

Jan 1, 1960

By Arthur Taggart

Recent jig practice has shown such marked departures from the pronouncements of the textbooks, particularly as to particle size recovered and size range of feed, as to make it desirable to reexamine the mechanism of jig action. This paper presents the results of such a study. The general conclusions of the Paper are: I. A jig bed is a bi-functioned as well as bi-parted body. The upper layer comprises a plastic stream moving slowly in a substantially horizontal direction from feed lip to tail board. It serves to rough out tailing and light middling and to pick up heavy middling and lift it out 01 the jig box. The lower layer acts as the ultimate separating means by absorbing concentrate and rejecting heavy middling. 2. The separating function of the lower layer is performed in three definitely diflerent ways, depending upon the relative sizes of the grains presented to it and those composing it. Experimental The experimental work consisted of close and long-continued visual observations of operating beds in a plunger jig, eccentric driven, and in determinations of the settling rates of various metal spheres through a quartz bed under various conditions of operation. Falling velocities were measured by an ingenious method devised by A. 6. Dorenfeld, a student in the Mining Department at Colum- bia. Spheres of different metallic alloys, 3/8-in. diameter, were cast with a short piece of fine copper wire frozen in to Serve for suspension-A short piece of black cotton thread was looped to the top of the wire to serve as an indicator. The set-up for a test is shown in Fig. I. The thread should be boiled, if necessary, to make it freely water absorbent. The piece of clean plate glass D is supported rigidly at the proper height in a vertical position. The white scale E is similarly supported behind the glass. At the beginning of a test, D is filmed with water by holding it (best with clean rubber finger cots) under running tap water. It is then clamped in approximate position and C, already wet, is laid across it and drawn straight and vertical with the upper end at or near the top of D, and the ball A slightly above the top of the expanded bed. The water film holds the string to the glass. For a test the string is released, its upper end position noted just after the top of the ball becomes submerged, when the corresponding time is read, and thereafter simultaneous readings of position and time are taken as desired. Results of the visual studies of the bed are given at the pertinent places in the following discussion. Results of the settling tests are summarized in Figs- 2 and 3. Definitions The name bed as used herein refers to the entire mixture of solids and water filling the jig box. A layer is a stratum of a bed composed of particles of substantially the same specific gravities. A granular product is long-range when it approximates a crushed or ground product limited as to upper size only; a short-rafzge product is one closely sized. A bed is loaded when operating with continuous feed and discharge of products; it is unloaded when pulsating norma11y but neither being fed nor

Jan 1, 1943

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio'nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.' All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

By C. R. Criss, R. J. McCormick

ThiS paper .summarizes the development and perform. ance of the Coldwater Oil field, Isabella County, Mich. Production is obtained at a depth of 3750 ft from a dolomite reservoir, which is probably both Rogers City and Dundee. There appears to be no persistent barrier to vertical fluid movement between the Rogers City and Dundee, and both formations are believed to have a common original oil-water contact. No we1ls are open to production at the level of the Dundee. The discovery of the field in 1944 was followed by the drilling of 81 producing wells and nine dry holes. By the end of 1952, the field had produced 12,763,000 bbl of oil, at which time 69 active wells were producing 3600 B/D oil and 21,000 B/D water. The reservoir has an effective natural water drive, and bottom-hole pressure has declined 75 psi from an original pressure of 1453 psi. Oil is undersaturated at reservoir conditions with a solution GOR of 512 cu ft/bbl and a saturation pressure of 1190 psi. INTRODUCTION Although the Coldwater Field is now in its ninth year of production, it ranks seventh in cumulative recovery, and second in current daily oil production in the State. Following complete development of the field in 1946, it has consistently contributed approximately 11 per cent of Michigan's daily production. Coldwater appears to have a greater pay thickness than most fields producing from the Rogers City forma- tion in the west central part of the Michigan basin. Except as influenced by the extent of closure and the thickness of the oil column, reservoir performance is believed to be representative of Rogers City fields in this part of the basin. For this reason, it is felt that the following presentation of factual data for the field will be of general interest. HISTORY AND DEVELOPMENT Discovery of the Coldwater field during Aug., 1944, followed favorable subsurface geological correlations and core tests drilled to a shallow stratigraphic marker horizon. The field is located in the west central part of the Michigan Basin in Coldwater Township (T16N-R6W), Isabella County. It is 60 miles west-northwest of Bay City, and near the geographic center of the southern peninsula of Michigan. The discovery well flowed 200 bbl of oil the first 24 hours from the Rogers City dolomite at a depth of approximately 3750 ft. Field production is principally from the Rogers City with a minor amount assumed to come from the underlying Dundee dolomite, although none of the wells are open to production at the level of the Dundee. Both the Rogers City and Dundee formations belong to the Devonian system (See Geologic Column-Fig. I.) In addition to Rogers City-Dundee oil production, sweet gas is produced from the Michigan Stray sand of the Mississippian system at a depth of 1400 ft. The gas reservoir has approximately the same areal extent as the underlying oil reservoir. Although gas production is an important feature of the Coldwater field, this report is concerned only with the oil reservoir. The productive area is approximately 3200 acres. The pool is developed on a 40 acre spacing pattern with wells drilled in the center of the north half of 40 acre tracts, except for a few off-pattern wells drilled along

Jan 1, 1955

By Arthur Taggart

Recent jig practice has shown such marked departures from the pronouncements of the textbooks, particularly as to particle size recovered and size range of feed, as to make it desirable to reexamine the mechanism of jig action. This paper presents the results of such a study. The general conclusions of the Paper are: I. A jig bed is a bi-functioned as well as bi-parted body. The upper layer comprises a plastic stream moving slowly in a substantially horizontal direction from feed lip to tail board. It serves to rough out tailing and light middling and to pick up heavy middling and lift it out 01 the jig box. The lower layer acts as the ultimate separating means by absorbing concentrate and rejecting heavy middling. 2. The separating function of the lower layer is performed in three definitely diflerent ways, depending upon the relative sizes of the grains presented to it and those composing it. Experimental The experimental work consisted of close and long-continued visual observations of operating beds in a plunger jig, eccentric driven, and in determinations of the settling rates of various metal spheres through a quartz bed under various conditions of operation. Falling velocities were measured by an ingenious method devised by A. 6. Dorenfeld, a student in the Mining Department at Colum- bia. Spheres of different metallic alloys, 3/8-in. diameter, were cast with a short piece of fine copper wire frozen in to Serve for suspension-A short piece of black cotton thread was looped to the top of the wire to serve as an indicator. The set-up for a test is shown in Fig. I. The thread should be boiled, if necessary, to make it freely water absorbent. The piece of clean plate glass D is supported rigidly at the proper height in a vertical position. The white scale E is similarly supported behind the glass. At the beginning of a test, D is filmed with water by holding it (best with clean rubber finger cots) under running tap water. It is then clamped in approximate position and C, already wet, is laid across it and drawn straight and vertical with the upper end at or near the top of D, and the ball A slightly above the top of the expanded bed. The water film holds the string to the glass. For a test the string is released, its upper end position noted just after the top of the ball becomes submerged, when the corresponding time is read, and thereafter simultaneous readings of position and time are taken as desired. Results of the visual studies of the bed are given at the pertinent places in the following discussion. Results of the settling tests are summarized in Figs- 2 and 3. Definitions The name bed as used herein refers to the entire mixture of solids and water filling the jig box. A layer is a stratum of a bed composed of particles of substantially the same specific gravities. A granular product is long-range when it approximates a crushed or ground product limited as to upper size only; a short-rafzge product is one closely sized. A bed is loaded when operating with continuous feed and discharge of products; it is unloaded when pulsating norma11y but neither being fed nor

Jan 1, 1943

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat' who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E' and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200'C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970

By F. Keller, E. H. Dix

The desirable high strength and hardness of the heat-treated strong aluminum alloys result from two distinct structural changes: (1) the formation of a solid, solution by heating at the required temperature for a sufficient period, and the substantial retention of this solid solution by rapidly quenching; (2) precipitation of particles of constituent and coalescence to a critical size to produce maximum strength and hardness. In alloys of the duralumin type, that is, alloys containing both copper and magnesium silicide precipitation takes place at normal atmospheric temperature, whereas in alloys containing copper without magnesium silicide or magnesium silicide without copper, maximum properties are obtained only after an accelerated aging treatment consisting of heating for 15 to 20 hr. at temperatures of about 150" C. The mechanical properties of these alloys subsequent to quenching but prior to aging are ideal for forming operations. Unfortunately, however, the alloys of the duralumin type age very rapidly during the first 24 hr. and aging is substantially complete after four days. For severe forming, such as the heading of rivets, it is desirable that this be accomplished within ½ hr. or at the most 2 hr. after quenching. Alloys containing magnesium silicide without copper also age at normal temperatures but the aging is less rapid and the material can be satisfactorily worked within several weeks after quenching. Some slight aging of alloys containing copper alone also takes place at room temperature but it is unimportant from the standpoint of workability. Any method of retarding the aging at room temperature of the duralumin type of alloys would be of considerable advantage in that the period during which the material could be worked successfully would be lengthened. For instance, in aircraft plants it is customary to supply the workmen with small lots of rivets that should be used within ½ hr . after heat treatment. Such procedure has the obvious disadvantage of being uneconomical, and furthermore there is always the possibility that the workmen would use the rivets after the time limit had expired, or the supply being depleted might use some that had not been heat-

Jan 1, 1931

By R. Maddin, S. K. Tung

SUCCESS of the dislocation theory in formulating the transitional lattice theory proposed by Har-greaves and Hill in 1929' is well established for low angle grain boundaries. The theoretical work of Burgersa and Read and Shockley,3 together with the experimental observations of Aust and Chalmers4 and Parker and colleagues,6 leaves little doubt as to the structure of grain boundaries with differences of orientations up to between 15" and 20". Beyond these angles, the structure of the boundary is not so clear, and is still a matter for conjecture. There have been notable experiments devised from which the data could be used to calculate energetics for possible arrangements of atoms in forming a large angle boundary.6 Most of these experiments deal with diffusion through and along the grain boundary. The recent work of Rhines and Cochart7 and Rhines, Bond, and Kissel18 was concerned with the relative movement of grains in aluminum bicrystals under constant tensile loads with their boundaries aligned at 45 " to the tension axis. The gliding along the grain boundary was cyclic and began after an incubation period. The velocity of gliding increased with the sum of the angular difference, 8, between the operative slip direction in the conjugate crystals and the angular difference between the active slip planes as measured between their traces upon the grain boundary. The initial gliding rate varied with temperature, and the logarithm of the average gliding taken over a considerable period was a linear function of the reciprocal of the absolute temperature: the slope gave an activation energy of 11,000 ±1,000 cal per mole. Since the rate of grain boundary shear is sensitive to the misorientation of the grains themselves, as shown by several workers,7,8 it is suggested that further work of this type might be fruitful in adding information regarding the behavior of boundaries under stress. The techniques devised by Chalmers" added impetus to the facility for observing grain boundary behavior, in that they provided a simple means for producing bicrystals of predetermined orientation so that the angle of the boundary could be controlled,

Jan 1, 1958

By R. J. Evans, A. G. Revesz

Silicon films have been grown by chemical reaction on (111) silicon substrates. The surfaces were examined by various microscopic and interfero-metric methods. Surface structures are classified into two groups depending on whether the angles between the bounding planes and the (111) surface are small (<3 deg) or large (> I0 deg). A layer-gvowth mechanism is postulated to explain the topography and the influence of growth parameters. Growth proceeds by lateral expansion of the (111) layers in (211) directions, thereby forming steps. The step edges are perpendicular to the direction of expansion and are thus along (110) directions. Step bunching md surface nucleation both play an important role in modifying the flow pattern and in the step regeneration. These are influenced ver?) much by impurities, especially oxygen. Although the growth is a result of a surface-controlled ga: reaction, it is very similar to growth from an impure solution. OVERGROWTH ("epitaxial growth") of silicon is important and widely used. During the past years several investigators have observed various topographical features or so-called faults on the grown films. A study of the surface morphology gives some insight into the growth mechanism. I) EXPERIMENTAL Silicon films have been grown on silicon substrates by a method described by Theuerer.&apos; Silicon is formed by reduction of SiCl, in hydrogen. The rate of incidence of SiC1, was varied between 5 x 10"6 and 2 x 10&apos;4 moles min-&apos; cm-&apos;. The mole fraction of Sic4 in the Hz-SiCL mixture was about 5 x X Both the rate of incidence and the mole fraction were calculated on the assumption that the Hz bubbling through the SiC1, reached equilibrium saturation. Assuming uniform velocity distribution, the linear velocity of the gas in the reactor tube was estimated to be 2 cm sec-l. The temperature of deposition was varied between 1070" and 1260°C. Chemically polished p-type silicon wafers of 20 to 100 ohm cm resistivity were used as substrates. These were within 1/2 deg of a (111) orientation. The thickness of the grown n-type film was determined by two methods: a) measurement of the depth of the p-n junction taking into account the junction shift due to diffusion, b) measurement of the traces of stacking-fault tetrahedra on the (111) plane.&apos; The agreement between the two methods was better than 20 pct. The rate of growth varied between 0.2 and 4.0 pmin-&apos;. The formed films were examined by reflection and light-section microscopy, and by multiple-beam interferometry. Phase-contrast illumination revealed height differences of about 30A. For measuring heights greater than 1 p a light-section microscope3 was used. The resolution by multipke-beam interferometry4 was between 50 and 100A. Crystallographic directions on the surface were determined by X-ray and from the orientation of etch pits and stacking faults as revealed by Dash etch (I part HI?, 3 parts HNOJ, and 12 parts CH3COOH). Some specimens have been investigated by electron microscopy. Platinum-shadowing and carbon-replica techniques were used to show the fine topography and reflection diffraction to determine the structure of the grown layers. 11) RESULTS The topographical features can be classified into three groups. he first group is comprised of fine ridges (striations). The second group consists of structures, which are bounded by planes making angles of less than 3 deg with the (111) surface. They are, therefore, vicinal planes. Structures which closely resemble growth or etch pyramids from the third group would normally be bounded by perfect low-index crystallographic planes. In this case they are deformed. The angles between the bounding planes and the (111) surface are generally larger than 10 deg. The fine ridges are present, even on the smoothest surfaces, as shown in Fig. 1. They are along a (110) direction. The height differences could not be resolved with interferometric techniques. The basic characteristic structures of the second group are depressions and hillocks. These are bounded by three planes, two of them with larger slopes than the third one. The edges between the planes, as projected to the (111) surface, point in (211) directions. Various habits of these structures are shown

Jan 1, 1964

By Ben-Zion Weiss, Melvin R. Meyerson

Chromium diffusion coatings on commercial Armco iron lead to carbide precipitation at the grain boundaries in and below the coatings. High compressive stresses are introduced into the coating and, as a result, tensile stresses are introduced into the base material below the coating. In coated samples, fatigue cracks form at the grain boundaries below the coating after only a limited portion of the total lifetime (5 to 10 pct). Residual tensile stresses and a stress concentration caused by precipitated carbides seems to be responsible for early crack nucleation. Stage I of Propagation may be divided into two substages: I-a in which the crack Propagates along grain boundaries, and I-b in which the crack propagates along slip boundaries according to a shear mode. In uncoated samples, the cracks form at slip bands after 40 to 50 pct of the total lifetime. In coated samples the Propagation process takes longer than in uncoated samples because of the moderate rate of crack extension until the crack breaks through the coating. The chromium-diffusion coating causes little if any increase in fatigue life. CHROMIUM diffusion is one of the most popular processes used to apply coatings to iron alloys. This popularity stems from the fact that the diffusion treatment is comparatively easy to carry out, and it improves certain surface properties such as corrosion and wear resistance as well as some other properties. Very little effort has been devoted to the investigation of the effect of chromium-diffusion coatings on mechanical properties and particularly on fatigue properties. Since the chromium coating usually represents a small fraction of the total volume of the base material it is generally assumed that the macro properties are dependent principally on the base material rather than the coating. Insofar as fatigue is concerned, there are indications that the fatigue life of the chromium coating is not less than that of the basic material and the fatigue properties are generally not reduced by it.&apos; But chromium diffusion causes drastic structural and chemical changes in the region of the material surface2-4 which introduce additional residual stresses. Such changes must affect fatigue crack nucleation and may sometimes affect the initial stages of propagation. Furthermore, it is conceivable that the secondary stages of the crack propagation could be influenced by some irreversible structural changes in the core of the material, which stem from the long-time heat treatment at high temperatures required to apply the coating. This paper analyses the structural and compositional changes produced in commercial Armco iron by a chromium-diffusion coating and the effect of the coating on fatigue crack initiation and propagation. EXPERIMENTAL PROCEDURES The investigations were carried out with commercial Armco iron. The chemical composition of the iron, the number of specimens tested, the grain size produced during chromizing and heat treating, and the thickness and microhardness of the chromized layers are shown in Table I. Samples were chromized by a gas diffusion process. The temperature and time of the diffusion coating process were chosen according to a previous grain growth study. It had been found that at a temperature of 970°C and a holding time of between 3 and 9 hr there are practically no changes in grain size. To describe the grain size more accurately the ASTM method5 was supplemented by a statistical analysis of the mean volume diameter as outlined by Fullman6 and The The mean volume diameter was deter- mined from D = p/2m where D is the mean volume diameter, and m is the mean reciprocal value of grain diameters as seen on the micrograph. The shape and the size of the asymmetrical sample, see Fig. 1, were chosen so as to facilitate the study of fatigue crack initiation. Before coating, the samples were machined and the surface of the groove was polished. After chromizing, the two side surfaces were machined and polished so as to retain the coating only on the top surface of the groove. Residual stress in the chromized layer was measured on the top of the grooved section of the specimen after the diffusion process. The inclined incident X-ray beam procedure was used.9&apos;10 The computations were performed with the initial assumption of a zero surface normal stress component. An electron microprobe analyzer was used to obtain the relative amounts of chromium and iron con-

Jan 1, 1970

By Jun Hino, P. G. Shewmon, P. A. Beck

THE investigations of Crussard,&apos; of Guinier and Tennevin,&apos; and of Dunn and Daniels," indicate that the subgrains formed in a cold worked and annealed metal are capable of growing at each other&apos;s expense during annealing, if the temperature of annealing is sufficiently high and the time is long enough. The results of Dunn and Daniels are particularly convincing in showing that subgrain growth is essentially the result of the free surface energy associated with the subboundaries. In subgrain growth, as in ordinary grain growth, energy is gained as a result of the decrease in total subboundary surface area per unit volume. Recently, Wood and Scrutton4 found that the rate of subgrain growth upon annealing increased very considerably, if simultaneously a creep strain was applied to the specimen at a low strain rate. Working with 99.98 pct pure fine-grained aluminum, these investigators found that the continuous X-ray diffraction back-reflection rings of material strained at room temperature remained continuous after heating for ten days at 250 °C. However, when heated at the same temperature under a stress of 1000 psi even for only three days, the formerly continuous X-ray diffraction rings broke up into numerous dots, which were fairly clearly separated from each other. The continuous X-ray diffraction rings were interpreted as indications of a very small subgrain size, not resolved by the X-ray diffraction method used. The breaking up of the continuous X-ray diffraction ring during annealing under stress was taken as an indication of a great increase in subgrain size, so that the individual subgrains could then be resolved. The effect of simultaneous strain at a low strain rate in accelerating subgrain growth, discovered by Wood and Scrutton and designated by them as "cell growth," is of fundamental importance. The experiments described in this note were carried out in order to confirm Wood and Scrutton&apos;s results by direct metallographic observation. Also, information was sought as to the minimum creep strain necessary to produce this effect. A fine grained high purity aluminum strip was prepared by alternate 33 pct rolling and annealing treatments for 1 hr at 350°C. Specimens cut from this strip were subjected to a relatively fast creep strain of 7.2 pct in 3.5 min at 300°C under a constant load initially corresponding to 1185 psi. The subgrains set up were large enough (about 0.015 to 0.03 mm) to be clearly observed (Fig. 1) at X200 magnification with polarized light, after electrolytic polishing and anodic etching, producing a fine oxide film." The corresponding X-ray diffraction pattern is shown in Fig. la. After the fast creep strain treatment a portion of the specimen was subjected to a creep strain of 8.3 pct in 44 hr at 350°C under a constant load initially corresponding to 320 psi. Another portion, annealed under the same conditions, but not strained, served as control specimen. The subgrain size of a typical area of the specimen annealed under strain and of the one annealed without strain is shown in Figs. 2 and 3 (X-ray diffraction patterns, Figs. 2a and 3a). Annealing without strain produced clearly observable subgrain growth (subgrain size: about 0.03 to 0.05 mm). The effect of simultaneous strain was to increase greatly the rate of subgrain growth (resulting in a subgrain size of approximately 0.05 to 0.13 mm), in accordance with Wood and Scrutton. In another experiment, the effect of the amount of simultaneous strain was studied. The initial subgrain structure was set up by fast creep, as described previously. The specimen was then heated at 350 °C under a constant load initially corresponding to 320 psi, as above, for 2.2 hr (0.24 pct strain), and 8.8 hr (0.58 pct strain). Comparison with the corresponding unstrained control specimens by means of X-ray diffraction showed that 0.58 pct strain definitely had an effect, but the effect of 0.24 pct strain was doubtful.

Jan 1, 1953