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By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,' in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By R. C. Hall

The magnetic anisotropy and magnetostriction of single crystals of alloys between 25 and 59 wt pct Co in Fe have been determined in the disordered and ordered states. The magrzetostriction is large and positive for all alloys in both states of order (up to 150 x 10-6 for A,, and 40 x 10-6 for 111). The magnetic anisotropy becomes zero rzear 41 pct Co for the disordered state. Ordering shifts the zero-anisotropy composition to about 50 pct Co. COBALT-iron alloys have for many years been of interest as magnetic materials because they have unusually high magnetic saturation values.' This interest was increased recently by the development of Supermendur.' Supermendur is an alloy of 49 pct Co-49 pct Fe-2 pct V* which was found by suitable purification and heat treatments, including a magnetic anneal, to possess excellent magnetic properties. These included a square hysteresis loop with a low coercive force and a high magnetization, and a low total loss. Two factors which are important in determining the magnetic hysteresis properties are the basic magnetic properties of magnetostriction and anisotropy. Alloys having zero anisotropy and zero magnetostriction show improved hysteresis properties.3 Since very meager data4-' are available in the literature on the single-crystal anisotropy and magnetostriction of the cobalt-iron alloys, the present program was undertaken to determine these two properties in the disordered and ordered states. EXPERIMENTAL TECHNIQUES Ingots of the cobalt-iron alloys containing from 25 pct to 59 pct Co in iron were vacuum melted from electrolytic iron and cobalt of 99.9 pct purity. The ingots were cooled at a rate of about 1°C per hr through the transformation temperature (950" to 980°C dependent on the alloy content) for the growth of large grains. From these grains, single-crystal disks were fabricated with either the (110) or (100) plane parallel to the faces of the disk. The crystals were given two heat treatments to produce either the ordered state (cooling rate of 20°C per hr from 850 "C) or the disordered state (water quench from 850 °C). Since the iron-cobalt alloys order very rapidly, the water quench may not have produced complete disorder in all cases. Due to the method of growth, the crystals were not perfect. Most of the samples had low-angle boundaries and a few had some small included grains. These imperfections could and probably did affect the accuracy of both the magnetic anisotropy and magnetostriction measurements. Much of the scatter in the data may be attributed to the crystal imperfections. The methods of determining the spontaneous saturation magnetostriction and the anisotropy have been previously described.419110 MAGNETOSTRICTION The magnetostriction in the [loo] and [Ill] directions (hO0 and ?111 respectively) is illustrated in Fig. 1 for the disordered state. Both ?100 and ?111i became large positive values as cobalt was added to iron. The state of order did not have a large effect on the magnetostriction. The effect of order did not appear too consistent in these data. Tentative curves are shown in Fig. 1 for the ordered magnetostriction near the FeCo composition; here ?100 appeared to be lowered and ?111 raised as the degree of order was increased. These results agree qualitatively with the

Jan 1, 1961

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

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

By B. H. Kear

Clustering of slip bands in different systems has been observed in both ordered and disordered Cu3Au crystals compressed in the <110> orientation. Certain features of the slip band patterns are explained in terms of reactions between dislocations with Burgers vectors at 120 deg; in a few rare cases, the slip band evidence suggests that the Products of such reactions form diffuse tilt boundaries between the differently slipped regions of the crystal, similar to the known behavior of ionic crystals, but not nearly so well defined. WHEN crystals with orientations favorable for multiple slip undergo plastic deformation, slip may occur in different systems in localized regions, so that clusters of slip bands are developed. This phenomenon has been observed in fee1-4 metals and also in ionic crystals having the sodium chloride structure.5-8 In the ionic crystals, the boundaries formed between the differently slipped regions of the crystal assume characteristic orientations and are associated with macroscopic tilts that are plainly visible on the sides of the crystal. Recently, this interesting feature was explained in terms of the formation of diffuse low-angle boundaries as a result of interactions between families of glide dislocations in the different systems meeting in the boundaries.9 This paper describes an attempt to obtain similar evidence for boundary formation in an fee crystal. The alloy Cu3Au was chosen for the present study simply because this material is currently being used in a general study of differences in deformation behavior of the ordered and disordered phases of this alloy, which will be described elsewhere. EXPERIMENTAL PROCEDURE The two specially oriented compression specimens used in the present study were prepared from a melt-grown single crystal by careful cutting, grinding and polishing. The finished specimens were about 6 mm by 2 mm in cross section by 6 mm tall, with their ends parallel to (101) and sides parallel to (111) and (121); the broad faces of the specimens were made parallel to (711). Both specimens were annealed in an evacuated quartz tube at 850oC for several hours, slowly cooled to 500°c, and then quenched into water in order to obtain the disordered state for the alloy. One of the specimens was partially ordered (with S- 0.8) by reannealing at 350oC for 100 hr. After these annealing treatments, both of the specimens were electropolished. 10 Finally, the specimens were compressed in the [loll orientation and their stress-strain curves were recorded. The deformation was carried out in increments of a few percent strain. At each stage in the deformation the specimens were unloaded, removed from the compression jig, and examined optically for slip bands. Before reloading, the specimens were repolished, so that the observed slip band patterns were characteristic of a particular stage in the deformation. EXPERIMENTAL RESULTS Fig. 1 show!; the stress-strain curves for the ordered and disordered specimens and also indicates the stages 1, 2, and 3 where the deformation was interrupted for examination of slip bands. The curves show marked differences in flow stress and in work hardening rate in the two specimens, as observed by previous workers.11,12 Also, it was found, in agreemement with the observations of Taoka and Sakata,&apos;3 that the plastically deformed disordered alloy showed the characteristic coarse slip bands of alloys, whereas the ordered alloy exhibited a fine slip band structure similar to that of pure metals. Slip Band Observations. In what follows, the description of the slip band patterns, with accom-

Jan 1, 1962

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and "{2,3,10)" or "(127)". (It is now thought1&apos; that the "{0,1,13)" habit reported for the Fe-Ni-C alloys&apos;&apos; is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove.&apos; The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and tj2 = vi (i = 1, 2, 3), the Kz qd 771 elements are given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics cij Iand cij reduce to the unit tensors 6ij and 6ij so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and 77~ are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4&apos;6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By C. Richard Tinsley

SUMMARY A detailed analysis of nickel, copper, and cobalt recovery from manganese nodules shows simple rates of return of 9-15% in 1985. A sulfur dioxide roast process yields a slightly better return than an ammonia leach technique. Nodule tonnage predictions tend to be over-optimistic and more conservative forecasts show that market penetrations are only significant for cobalt and manganese. However, cobalt prices are unlikely to fall to the level of nickel. Between now and 1985, cobalt is expected to be in balanced to tight availability. INTRODUCTION Deep-ocean manganese nodules are one- to two-inch concretions which cover 2040% of large areas of the ocean bottom. Commercial targets far these black, potato-like nodules are located in the North Pacific at water depths of 5,000-6,000 m. in a belt roughly midway between Hawaii and Mexico. However, good grade nodules are not solely limited to this belt as areas southwest and northwest of Hawaii, as well as in the Indian Ocean, contain concentrations of acceptable grade manganese nodules. Some 90% of the nodules are found half-buried on the deep ocean bottom. A siliceous-ooze host soil combined with low sedimentation rates, certain ocean currents, and possible geo- thermal effects are favorable factors far nodule formation. The viewpoints and analyses in this paper are the author&apos;s own and should not be attributed in any way to Amoco Minerals Co.

Jan 1, 1976

By I. L. Greninger

THE property of the Andes Copper Mining Co. is in the central part of the Republic of Chile, Province of Atacama, 147 km. (91.5 miles) eastward by rail from the port of Chañaral. At this point the Andean system is made up of two principal ranges. The mine is on the westerly slope of the outer, or western, range, at a mean elevation of 3250 m. (10,500 ft.). A meter-gage railroad extends from the company&apos;s port at Barquito, near Chañaral, to the reduction plant at Potrerillos. This road has a total length of 151 km. (94.0 miles), of which 93 km. (57.79 miles) are owned by the Andes Copper Mining Co. The remainder of the road is owned by the state. The company operates its trains over the portion of the road owned by the state, under an agreement with the Chilean Government. The mine is connected with the reduction plant by a meter-gage railroad, 10 km. (6.214 miles) long, which extends from the coarse ore bins at the metallurgical plant to the underground storage bins at the mine. Tunnels make up 60 per cent. of the total length of this railroad. As is characteristic of the Andean region in Chile, the topography of the locality is extremely rough, and a number of points near the mine have elevations of from 15,000 to 16,000 feet.

Jan 1, 1928

By E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.&apos; Recent work&apos; indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken&apos;s 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. &apos;V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

By George Rupp

THE Sunrise iron mine of The Colorado Fuel and Iron Corporation is in Platte County, Wyoming, about 110 miles north of Cheyenne. It is served by the company-owned Colorado and Wyoming Railway, which connects with the Chicago, Burlington and Quincy and the Colorado and Southern railways at Guernsey, Wyoming, a distance of 6 miles from the mine. The original Sunrise claims were staked mainly by United States Army officers and soldiers stationed at old Fort Laramie, because of small showings of copper in the Carboniferous limestones that form a horizontal capping overlying the Huronian iron ore. A small copper smelter was operated for about three years at Fairbanks, now an aban-doned town on the North Platte River. As many of the copper shafts and test pits near the present Sunrise mine were deepened, they pene-trated the capping and encountered iron. ore or gray sericitic schist, and were abandoned. Evidence of an early interest in iron ore was found when the Chicago claim was stripped for mining. A narrow, winding crevice was dis-covered, which led downward 20 ft. through the capping to the underlying soft red hematite, in which a room 10 by 14 by 7 ft. had been excavated. Stone hammers and wedges and a few rusted pieces of iron were found on the floor, and the evidence is conclusive that the excavation was used up to rather recent times by Sioux Indian medicine men, to provide war paint.

Jan 1, 1939

By Warren Blauvelt

IN VIEW of the enormous wastes of natural resources, of labor and of capital, due primarily to the economic environment, established by legislation, the general neglect of this phase of the problem of the elimination of waste is difficult to understand. In such a study, the engineering method of attacking a problem should be employed. The engineer does not try to solve his problem by disregarding natural laws, but by utilizing them. The successful engineer establishes an environ-ment in which forces, acting in harmony with natural laws upon an object or objects, will produce the desired results. The engineer who notices that the water level in a vessel, into which a gallon of water per minute is flowing, is two feet higher than the level in an adjacent vessel, connected therewith by a 6-in. pipe, does not assume that the law of gravity has ceased to work, or that water no longer seeks its level; he examines the connecting pipe for obstacles which prevent the free flow of water. Some editors, many reformers and most politicians tell us that the law of supply and demand no longer works; hence governmental control of commerce is necessary. Governmental control may temporarily-that is, until trial proves its futility- "insure domestic tranquility" and "promote the general welfare;" but it cannot "secure the blessings of liberty" which it cur-tails, nor can it "establish justice" which it violates.

Jan 9, 1922

J. B. Cohen (AVCO Mfg. Co.)-The model presented by the authors is only one of several possible mechanisms for low-temperature aging. It is true that the motion of dislocations to the copper atoms, followed by diffusion along the dislocation lines, is one such mechanism. However, the details of such a process which would :result in copper-rich platelets on (100) planes in the f.c.c. matrix are not clear. Furthermore, there is at least one other mechanism that may be used to e.xplain the authors&apos; results, so that the data do not clearly favor the Turnbull model. The zones may form by "normal" diffusion. The diffusion constants would be higher at room temperature than extrapolated data would suggest due to vacancies trapped in the specimens in the quench. The diffusivity would then be multiplied by the ratio of the number of vacancies present at the solution temperature to that present at room temperature. These vacancies could remain in the alloy specimen for long times at room temerature, due to interaction with the copper atoms. &apos; The activation energy for diffusion is smaller than that for bulk diffusion at elevated temperatures for it is only that for the motion of vacancies existing after the quench; after these are used up, the aging process effectively ceases. It is somewhat questionable if the laws governing transformation kinetics can be directly applied to changes in elastic moduli, especially in the case of aging where the structure and the composition of the zones may be changing during aging, If such laws are assumed, it is possible to explain the exponential factor of % with this vacancy model. It is probable that the structure of the zones and the matrix match only on (100) planes. Certainly the precipitates that form in this system after various aging treatments show orientation relationships similar to those of the zones. Strains on the edges of the zone may set up fields which do not allow the zone to grow in an edgewise manner. The exponent in the growth of a thin plate in a direction perpendicular to its face would be %. It may also be that copper atoms are attracted to dislocations. If this is the rate-controllin factor in the growth process Ifthisthen an exponent of % or % may arise. The writer would like to know if the authors have tried plotting l/a; proportional to as might be expected for "dislocation drainage." R. H. Doremus (General Electric Research Laboratory)—An important new method for following the growth of Guinier-Preston zones is presented in this paper, and I wish to congratulate the authors on their experiments. Their interpretation of the results, however, is doubtful in certain respects. To determine the exponent m in Eq. [4] the authors plotted -log at against t to various powers (their Fig. 6). The initial value of frequency used for these plots was found by extrapolating the data to zero time. In Fig. A the data from their Fig. 2 are plotted against a linear, rather than logarithmic, time scale. To obtain graphs similar to their Fig. 6 for these data one must use an initial frequency of about 52720; such a plot for m = % is shown in Fig. B. The straight line in Fig. B fits the data in an intermediate range only. The curve drawn in Fig. A was mapped from this line; comparison of

Jan 1, 1960

By W. W. Mason

The US began exporting coal in the late 1800s, at first in very small quantities to Canada and, beginning in 1897 and 1898, to the east coast of South America. Shipments to European countries began on a very limited basis in 1902 and these shipments increased gradually until World War I when shipments overseas increased from 7.3 Mt/a to 20 Mt/a. After the war exports dropped as fast as they had increased and, with the exception of exports to Canada, remained at very low levels until just after World War II when the US again emerged as a major coal exporter. World War II left the coal industries of Europe in ruin. As the US was the only country able to supply large quantities of coal at reasonable prices needed for reconstruction of the European economy, the US coal exports overseas expanded rapidly to 38.6 Mt in 1947. Additionally, we shipped 23.8 Mt of coal to Canada in that year for a total export of 62.3 Mt. Unfortunately, that level was not reached again until 1957 when exports reached an all-time high of 69.3 Mt - a high that has not been reached since. Over the years the level of US coal exports has fluctuated fairly widely. Approximately 80-90% of all US coal exports are high quality metallurgical grade coal so our exports level depends directly on world-wide economic conditions and world steel production levels.

Jan 1, 1982

By Shiou-Chuan Sun

Most previous work on sedimentation of coal1 and mineral2,3 suspensions has been conducted in graduated 1-liter glass cylinders of 6-cm diam. With this type of large container it is often difficult to see through the suspension and tedious to perform a large number of tests. Furthermore, the heavy glass walls and the graduation lines of glass cylinders cause internal and stray reflections, respectively. To obviate these difficulties, an Atlab Emulsion Viewer from Arthur H. Thomas Co. was adopted as an alternative apparatus. Equipment: The viewer,4 shown in Fig. 1, consists of: 1) a stainless steel frame rack holding 21 flat-bottom Nessler tubes or an ungraduated replica 1.64 cm ID and 1.80 cm OD, 2) a movable masked 150-w lumaline lamp behind the tubes, and 3) a scaled glass panel with 100 vertical divisions in front of the tubes. The tubes are snugly held by springs in slots formed by spacer bars, which also serve as shields to eliminate stray light. The lumaline lamp is mounted behind a slit in a movable housing so that it can be positioned behind the suspension to be examined. The lowest or 100-division line on the front glass plate is leveled with the upper side of the bottom of all tubes. The scaled portion of each tube, roughly 19 cm high and 40 ml in volume, is used to study coal and mineral suspensions.

Jan 1, 1959

Geological and Natural History Survey of Minnesota, Minneapolis, Minn W. H Emmons, Director A list of publications will be sent upon application Orders for publications should be addressed to The University of Minnesota Press, Minneapolis, Minnesota The Geological Survey of Minnesota has a record of long and useful service Some of the papers published have been outstanding in their field A series of 24 Annual Reports, covering the years 1872 to 1895-98, inclusive, was issued, of which 16 are still available at a price. More important however, are the six volumes of Final Reports, in which is collected the material presented in the earlier Annual Reports. All the strictly geological papers are found in four of the volumes of the Final Reports. vol 1 (1872-1882), principally geology by counties, 2 (1882-1885), same as 1, 4 (1896-1898), same as 1, 5 (1898-1900), Structural and petrographic geology Prices for each volume, leather $3, cloth $2 50, excluding postage, unless other directions accompany the order, volumes of the Final Reports will be sent express collect. A series of Bulletins has been issued, of which a few are out of print. Considering only those available, and of greatest interest, they are: Bulletin 5, Natural gas in Minnesota, by N H Winchell (1889), 50 cents, 6, Iron ores in Minnesota, their geology, discovery, development, qualities and origin, by N H Winchell and H V.

Jan 1, 1933

By L. G. Austin

INTRODUCTION Autogenous (including semi-autogenous) grinding has probably been the most important single innovation in milling practice for the last twenty years. However, the design of these units has been largely a matter of trial-and-error, since the normal empirical laws for the design of ball mill circuits do not apply with exactitude to autogenous grinding circuits. There have been examples of autogenous mills failing to achieve output or product specifications. It is worthwhile, therefore, to attempt to develop a more detailed and precise set of design laws, using the concepts of specific rates of breakages and daughter fragment distributions (1), and performing mill simulations by computer. This type of approach has been applied to ball and rod milling (2, 3,4,5), but even for these mills it is by no means complete as yet (6), because of the amount of experimental work involved. There has not been a strong incentive for industry to develop new design procedures in ball and rod milling because the prior back-log of experience with these mills makes for easy design by empirical comparsion with existing systems. The new approach has been followed mainly by University groups (7,8,9,10), although experience in Australia (9,11) has shown the advantages of the approach. Stanley (12) has applied the approach to results from a large autogenous mill, and we will use many similar concepts to his work, but extend the concepts to a more

Jan 1, 1977

Roof Bolts An expansion shell and plug Westinghouse roof bolting assembly made for use with threaded steel rods and large flat washers or steel channel employs a plug larger in diameter than those for trolley wire service. The notched plug helps prevent shell and plug from turning. The unit is shipped complete. Circle No. 1 Fan The Jeffrey Mfg. Co. Aerodyne Midget fan is a self contained blower or exhauster for auxiliary ventilation through tubing. Operating rating with 5 hp motor is 6.5 in. maximum static pressure, and 6200 cfm free delivery volume. Weight is 340 to 475 lb and it may be furnished in open or permissible form. Circle No. 2 Heavy-Density Initial installation in the Mesabi Range country of the Wilmot-Daniels heavy-density concentrating system was a 175 ton per hour plant at the [ ] Skubic Bros. Virginia, Minn., operation. This Wilmot Engineering Co. unit has a separatory vessel providing unidirectional medium flow and as the only moving part uses a standard drag-line conveyor for lifting sink out of the bath. Circle No. 3 Portable pH Meter A low priced battery-operated portable pH meter of utmost simplicity announced by the Photovolt Corp. uses only 3 ordinary radio batteries which give over 2000 hours of service. Accuracy of 0.03 pH is claimed by the manufacturer for the model 125, and AC power line supply is available. Circle No. 4

Jan 1, 1952

By N. F. Fiore, M. C. Mangalick

DISLOCATION damping in single crystals is orientation dependent.&apos; If dislocations are distributed uniformly over all the slip systems in a crystal, and if each dislocation contributes identically to the damping process, then a damping loss or decrement 6 arises. In fact, however, for a crystal of axial direction (hkl), dislocations on certain slip systems are oriented to make a larger contribution to the damping loss than are dislocations on other slip systems. Thus the measuring damping, 6 (hkl) is proportional to an orientation factor (hkl), which weights the ability of each slip system in the crystal to contribute to the total damping. If it is assumed that dislocations are distributed uniformly on all slip systems, then for a given orientation of an fcc crystal this factor is determined2,3 by the three nonzero elastic constants Cll, C12, and C44 and the density p. In this communication measured values of elastic constants for two Fe-18Cr-Ni alloys are reported, and the dislocation damping results on two different orientations of each alloy are analyzed for orientation dependence. Elastic constants were determined by measuring the ultrasonic velocities of one longitudinal and two shear waves in (110) direction of the fcc crystals.4 Variation of velocities with the change in orientation is very small for (110) orientation,3 and so this direction is ideal for orientation factor and comparative damping measurements. Experimental Procedures. The nominal compositions of the alloys studied are given in Table I. These alloys were vacuum-melted and vacuum-cast from high-purity materials at U.S. Steel Applied Research Laboratories. The single crystals were grown by the modified Bridgeman technique. The specimens were homogenized at 1350°C for 20 hr, cut to shape and size with a spark cutter, and then annealed at 1100°C for 20 hr prior to use. In the KHz frequency range, the Marx composite piezoelectric oscillator was used to obtain the damping. The ultrasonic pulse technique was used to measure the ultrasonic velocities and the attenuation in the MHz frequency range. M.c.mANGALICK,-- StudentMemberAIME,formerly Research Assistant, University of Notre Dame, is now with Casting Laboratory, Chase Brass and Copper Co., Cleveland, Ohio. N. F. FIORE, Associate Member AIME, is Assistant Professor, Department of Metallurgical Engineering and Materials Science. University of Notre Dame, Notre Dame, Ind. This communication is part of a Ph.D. thesis presented by M. C. MANGALICK to the Graduate School of the University of Notre Dame. Manuscript submitted May 20. 1968. IMD Elastic Constants. Table I gives the values of the ultrasonic velocities. Values of C11, C12, and C44 calculated from these velocities are also given in Table I, and it is evident that there is very little variation in C11, C12, and C44 with nickel content. This slight variation may be attributed to inaccuracies in velocity measurements and practical differences in the orientations of the specimens. For example, in B the time interval for vl was 2.4 ± 0.05 sec giving an error in v1 of 0.235 x or 0.005 in. per sec. The elastic constants obtained by pulse technique were tested by calculating E<110>, Young&apos;s modulus for the (110) direction, from the equation: This value was compared with the value computed from the resonance bar measurements in which where fr is the resonance frequency and I, is the length of the specimen. In all cases, the values calculated from the ultrasonic velocity measurements

Jan 1, 1969