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By C. Pin, J. Bruce Wagner

In order to demonstrate the role of defect chemistry in the solid state to a process-metallurgy reaction, laboratory experiments were carried aut to remove copper from liquid lead using lead sulfide which had been doped to provide definite concentrations of cation vacancies. The removal of copper decreases in the order: bismuth- or antimony-doped PbS, undoped PbS or tin-doped PbS, and silver-doped PbS. The data are explained using the simple mass -action law and in terms of the exceedingly rapid interstitial diffusion of coppw in PbS to vacant cation sites. Results are in agree-ment with thermodynamic predictions and certain industrial practices that copper may be removed from lead below the limit of its coexistence with pure Cu,S and pure PbS. The role of defects in solids has been exploited in semiconductors and many device applications, in explaining tarnish formation, dissolution rates, and mechanical properties. The application of these principles to many process-metallurgical problems has not received as much attention. It was the purpose of this study to illustrate the role of defect structures of solids in a process-metallurgical application. When lead is refined, the ore, galena (PbS), is reduced by a series of operations to liquid lead (lead bullion) containing impurities such as copper, bismuth, antimony, arsenic, and silver depending on the original composition, the fluxes added, and the particular type of operation, see Fig. 1. In order to produce a pure lead, a series of refining operations are carried out. A typical lead-bullion analysis before drossing is shown in Table I. Copper is removed first as its presence increases the zinc consumption during the desilverizing process. For preliminary copper removal the lead bullion is brought to a temperature of 440°C in a kettle of 60 metric tons capacity. Some tar (or sawdust or resins) is usually added and the kettle is cooled slowly to 400°C while the liquid is stirred. A solid phase, called a dross, floats on top of the liquid and the particles of the solid phase adhere to the tar. This "hot dross" is collected. It contains mostly lead and copper which are partly oxidized and/or sulfurized if the lead bullion contains some sulfur.*

Jan 1, 1963

By Robert E. Allen

The organized curtailment of California oil production is not yet one year old but during its first year it has accomplished so much that it is now firmly established as an agency of economic efficiency. The principle of cooperative curtailment has been adopted by other states and it is safe to say that the principle will continue as long as the demand for petroleum is notably less than the potential production. It' is interesting to note that this same principle of regulating supply to meet demand is now being urged for other industries, such as agriculture and mining. Since Oct. 31, 1929, when curtailment was instituted by the oil producers of Santa Fe Springs and Long Beach in an effort to avert the disaster of ruinously low prices which confronted them, there has been a constant and increasingly effective curtailment program in California. Prior to that time a notable effort toward the restriction of oil production was made under the direction of F. C. Van Deinse during the early summer months of 1929. A considerable reduction of oil output was recorded as the result of this effort, but because of incomplete cooperation and the discovery of still deeper zones at Santa Fe Springs the effort was abandoned; flush field production became unrestrained and prices soon fell to low levels. This initial curtailment movement was educational and experimental. It showed all operators a way out of their overproduction difficulties and developed the principles followed in later curtailment efforts. Thus it was that only a few days after their oil had been reduced to 60 c. per barrel, the operators of Santa Fe Springs got together and agreed to restrict their current production of more than 270,000 bbl. daily to not more than 150,000 bbl. daily. The operators at Long Beach followed the same course a few clays later and agreed to limit their production to not more than 110,000 bbl. daily. The Santa Fe Springs operators chose H. P. Grimm as umpire and director of their proration program. Neal H. Anderson was chosen umpire for Long Beach. Since that time, as the need for curtailment has increased, practically every field of the state has come under the curtailment of these two umpires. Curtailment of the Elwood and

Jan 1, 1931

By D. Turnbull, R. E. Cech

THE supercooling behavior of pure liquid metal droplets has been described.' The solidification behavior of small droplets of Cu-Ni alloys as a function of composition is described herein. The Cu-Ni system is of interest for such an investigation because the components are miscible in all proportions in both the liquid and solid state and the phase diagram of the system, Fig. 1, is a type often encountered in metal systems. It was noted by Van Riemsdyk2 and others that the nature of the "blick" of gold droplets during assaying is not perceptibly affected by the content of the platinum group metals that are soluble in both liquid and solid gold. With the exception of these very qualitative observations there appear to have been no prior investigations of the supercooling of alloy droplets. A series of nine alloys varying in composition by 10 pct (nominal weight) steps was made using certified OFHC copper, 99.996 pct purity, obtained from the American Brass Co., and electrolytic nickel pellets, 99.92 pct purity, obtained from the International Nickel Co. The alloys were melted and cast in vacuo in a high frequency induction furnace. Segregation was minimized by chill casting into 1-in. diam steel molds. Each alloy rod was homogenized at a temperature 50°C lower than the solidus for 100 hr in dry hydrogen. Samples for solidification experiments and chemical analysis were machined from the same portion of each rod and at a depth of in. from the rod surface. A Car-boloy tool was used in taking turnings to minimize contamination of sample by the cutting tool. As a check, a number of samples for microscopic observation were chipped from the ingot with a fragment of pyrex glass. The resultant data in all cases agreed, within experimental error, with the data obtained from machined turnings. A number of small particles, 30 to 50 micron diam, of a Cu-Ni alloy were placed in a quartz vial 1/32 in. diam x % in. long. This was inserted into a platinum ribbon heater and mounted in a high temperature microscope stage. The general procedure followed in inserting samples into the stage and measuring the temperature of melting and solidification was the same as described in an earlier paper.' A chromel-alumel thermocouple was used to study alloys of 88.93 pct Cu, 80.62 pct Cu, and 72.27 pct Cu. A platinum-10 pct rhodium thermocouple was used for the remainder of the alloys. Procedure The assembled high temperature microscope stage was first evacuated and the sample given a 2 min in situ treatment at 900 °C in dry hydrogen to remove surface oxides which might otherwise catalyze crystal nucleation. After this treatment the atmosphere was changed to purified helium and melting and solidification were observed microscopically. It was not possible to determine the solidus with certainty. However, the liquidus temperature was measured very accurately since the surface of the particle changed in appearance from coarse and uneven to smooth, mirror-like within a few degrees. The visually determined liquidus temperature was checked by finding the highest temperature to which the particle could be heated such that it did not supercool upon lowering the temperature. This temperature which checked within experimental error with that found by observing surface change was assumed to be characteristic of the thermody-namic liquidus. In order to minimize the effect of selective evaporation of copper from the alloy, samples were changed frequently and the droplets were heated no more than 50 °C in excess of the liquidus temperature T,. When the latter conditions were fulfilled, T, values were reproducible. After melting, the temperature was decreased slowly until the particles solidified. The sudden release of heat of fusion on solidification caused the

Jan 1, 1952

Arthur Jarman, Sydney, New South Wales, Australia (communication to the Secretary*):—All designs for modern metallurgical and chemical laboratories should provide each student's desk with a hood or cupboard for the removal of fumes, but I doubt the advisability of placing air-baths and similar apparatus close to the hot plate. It seems to me that unless the draft be exceptionally strong the fumes from ordinary wet assay work will corrode the iron-work of the fittings, in which case the baths would have to be removed to a general desk in order to lighten the work of the laboratory attendant. Since the laboratory described by Mr. White has been in use for two years, I should like to ask if any inconvenience has resulted from this corrosion. If not, it is certainly an important improvement to have the air-baths and similar apparatus placed on the student's desk. The hoods described by Mr. White are supplied with a good draft by means of a fan, which gives them a great advantage

Jan 1, 1905

By H. F. Gossenberger, J. J. Tietjen, J. J. Gannon, C. J. Nuese

External quantum efficiency measurements at 300" and 77°K are presented for vapor-grown GaAs and GaAs1-xPx electroluminescent diodes as a function of junction depth and doping. In GaAs, external efficiencies are found to decrease exponentially with increasing junction depth, defining an average absorption coefficient of 900 cm-1 at 300°K and 350 cm-1 at 77°Kfor epitaxial layers of p-type GaAs. It is shown that photon absorption losses dominate at room temperature and, in fact, account for most of the external efficiency degradation between 77° and 300°K. Healever, the internal ('junction) quantum efficiency is also found to decrease by a factor of 3.5 between 77" ALTHOUGH rapid progress has been made in recent years with GaAs, Gap, and their alloys for use in electroluminescent diodes, there are still important unknown factors related to the performance of these de- and 300°K. The dependence of GaAs efficiencies on donor and acceptor concentrations is presented, illustrating best efficiencies at donor concentrations of 1.5 to 2x 1018 cm-3 . External efficiencies are found to be independent of acceptor concentrations less than 3 x 1019 cm-3 but to degrade at higher doping. The fabrication of GaAsi-xPx electroluminescent diodes is briefly discussed. External efficiencies here for planar uncoated diodes are about 0.035 pct at 300°K and 0.4 pct at 77°for x = 0.42. A brightness of about 8500 ft-Lamberts is attained at 77°K and of 315 ft-Lamberts at 300° K. for curvent densities of 10 amp per sq cm. vices. For example, although the external efficiency is known to decrease by factors of typically 10 to 30 between 77°K and room temperature, the exact causes of this are still uncertain. Experimental results of ill' and carr2 with zinc-diffused electroluminescent diodes suggest that this external degradation is almost entirely due to increased absorption losses at room temperature, with a relatively temperature-independent internal efficiency; recent calculations by Gonda et al.3 corroborate this hypothesis. In contrast, Pilkuhn and Rupprecht4 find the internal efficiency of solution-grown GaAs laser diodes to degrade from 100 to 66 to 40 pct as the temperature is increased from

Jan 1, 1969

By A. G. Buyers, J. Chilton, W. E. McKee

STUDIES in the high-temperature separations chemistry of thorium-uranium fuels are complicated by the corrosive nature of these molten metal systems at 1700°C. Separations research pointed toward the removal of fission products from irradiated alloys has included a frozen salt-bed technique which minimizes container reaction with molten metal. The procedure consists of high-frequency induction melting of the metal sample which is supported by a vertical column of unmelted salt. The molten alloy melts its immediate salt environment and as it slowly falls down through the column, many of the fission-product poisons are transferred into the fused salt environment. The molten salt-metal zone is encompassed at all times by unmelted salt, preventing container contact. EXPERIMENTAL Experimental methods were separated into three parts: salt-bed preparation, melting, and analytical evaluation. A) Bed Preparation—The procedure for casting calcium-fluoride briquettes was to compress the powdered salt at 5,000 to 10,000 psi and place this compact in a graphite crucible. This assembly was inserted into a vacuum system and surrounded by an alumina crucible as well as molybdenum, tantalum, or stainless-steel foil thermal-radiation shields. The pressure was reduced and the crucible heated under vacuum to about 800°C with the fore pump operating. Argon was then admitted to about 0.8 atm and heating continued until the CaF2 had melted 5 min at the melting point seemed satisfactory). Apparatus used included a 1-in. graphite crucible with 1/8-in. walls, 1-in. ID in a 2-in. induction coil, and a 6-kw Ajax high-frequency converter. B) Melting—Calcium-fluoride briquettes, 1 in. in diam and 1/2 to 1 in. thick, were prepared and vertically stacked to obtain the desired column length. An irradiated alloy sample (nut = 10") was placed on top of the salt column and the assembly was connected to the vacuum system. After evacuation of 5 to 10 , purified argon was admitted and the system flushed twice. The final argon pressure was about 0.8 atm. The sample was heated by induction at a power of about 6.5 kw. It then melted its way down through the salt and freely dropped into a small alumina crucible. The molten metal is followed during its downward course by the induction coil which is mounted upon a power-driven machine-threaded shaft. Experimental conditions used in the foregoing work

Jan 1, 1960

By Carl Zapffe

The object of the Bradley process is to free manganese oxide from its associated gangue and separate the contained iron oxide by dissolving the manganese and precipitating it from the solution. This results in producing two oxides as concentrates, the one to be converted into a manganese sinter and the other into an iron sinter. The manganese sinter may be made to contain as high as 70 per cent. inanganese and as low as 1 per cent. silica, with phos'phorus not to exceed 0.02 per cent, and from that figure downward to about 0.005 per cent., and with sulfur at 0.007 per cent. The iron sinter contains about 2.50 per cent. manganese, making the total recovery of the manganese 98 per cent. The method involves selective roasting, which converts the manganese into a form in which it is soluble in an aqueous solution of ammonium sulfate, then precipitating the manganese as a hydrate by using ammonia gas, then stabilizing and washing the hydrate, followed by sintering; concurrently most of the iron oxide is converted by roasting into an insoluble form and becomes a residue with magnetic qualities, which makes possible the recovery of much of the iron in the ore. Leaching manganese by using sulfur dioxide gas was shown possiblc Inany years ago. Mr. Bradley tried it for a year, working in conjunction with the original experimenters of that method, and found that while relatively pure inanganese oxide could be produced, the likelihood of developing a commercial process along this line was not very encouraging. He also attempted leaching with nitric and sulfur acids, but the cost of recovery mounted and the quality of the product was not as good Mr. Bradley tried nearly every leaching method proposed, and the expen-ments were made on a large scale in the spacious laboratories of John C. Wiarda & Co., in Brooklyn, N. Y. Insufficient encouragement was discernible in the results obtained. Upon the suggestion of N. Arthur Laury, of John C. Wiarda & Co., Bradley undertook using arnrnoniurn sulfate. Because a high rate of recovery appeared feasible, Bradley planned the erection of a 4-ton pilot plant at the State of Minnesota Mines Experiment Station, at Minneapolis. The results of that work are described in this treatise.

Jan 1, 1929

The official Institute reports for the year 1929 were distributed in pamphlet form at the Annual Meeting, February, 1930, and were later included in Section 2 of Mining and Metallurgy, June, 1930, and thus made available to the entire membership. Membership In its report the Admissions Committee set forth the changes in membership during 1929, as follows: Total membership, Jan. 1, 1928, 8582; elected and placed on rolls in 1929, including 59 reinstatements, 509; loss by resignations in 1929, 88; loss by death in 1929, 110; loss by suspension in 1929, 37; membership at end of year not including Student Associates, 8856. Distribution of membership: Honorary Members, 16; Members, 6590; Junior Members, 38; Associates, 1041; Junior Associates, 1033; Rocky Mountain, 138; total membership, Jan. 1, 1930, 8856; Student Associates, 150; total including student associates, 9006. Treasurer's Annual Report, Year of 1929 Statement of Receipts For the year ended December 31, 1929 Dues: Arrears............................................ $ 3,501.75 Current............................................ 97,257.12 New Members...................................... 5,721.50 Advance........................................... 1,970.79 $108,451.16 Initiation Fees.................................................. 7,436.OO Magazine Receipts: Advertising Gross Receipts........................... $40,610.81 Magazine Sales..................................... 3,799.84 44,410.65 Sale of Transactions Current........................... $ 2,985. 15 Sale of Special Editions Current........................ 5,147.82 Sale of Back Transactions and Special Editions........... 4,186.93 Sale of Year Book..................................... 65.50 Sale of Authors' Reprints.............................. 2,585.40 Sale of Pins and Fobs.................................. 14.73 Sale of Technical Publications.......................... 1,451.55 Sale of Bindings...................................... 3,949.13 20,376.21 Net Interest Received: On Bank Balance and Temporary Investments......... $ 2,595.04 On Lie Membership Fund........................... 3,223.43 On James Douglas Library Fund...................... 5,425.61 On General Reserve Fund............................ 2,015.58 13,259.66 Miscellaneous Receipts........................................... 335.80 Total Receipts................................................ $194,269.48

Jan 1, 1930

By N. Brown, H. Green

The effect of quenching temperature and of aging temperature and time on compression stress-strain curves of ß brass was investigated. Age softening occurs at a rate which decreases with decrease of quenching temperature below the critical temperature for ordering. The activation energy for softening is 15,400 cal per mol. No matter how rapidly brass is quenched or what the temperature from which it is quenched, practically complete order is obtained at room temperature. It has been demonstrated that with respect to the specific heat,',' electrical resistivity," X-ray diffraction, and microstructure, the slowly cooled and rapidly quenched specimens are the same and that complete long range order exists in both cases. However, Smith" showed that the hardness of ß brass depended upon the cooling rate and the temperature from which brass is quenched. Smith showed that the hardness was a maximum for specimens quenched from about 445 °C and that the as-quenched structure softened at room temperature at a rate depending upon the temperature prior to quenching. This softening after quenching is in this paper referred to as age softening. The results of this investigation are qualitatively the same as the findings of Smith. However, a more detailed analysis of these phenomena has been possible since the stress-strain curve offers a more sensitive index of the state of the metal than hardness. It is the purpose of this paper to show how the mechanical properties are related to the ordering of ß brass. A 200-lb ingot made from electrolytic copper and electrolytic zinc was extruded to 1/2in. rod. Chemical analyses at frequent intervals along the rod showed that the alloy contained 51.5 pct Cu with the greatest impurity being iron, at 0.01 to 0.001 pct. To obtain a constant test material, the 1/2in. extruded rod was warm-rolled to % in. diameter at 200°C and then recrystallized to a grain size of 2.0 mm. The specimens for the compression test were % in. high and % in. in diameter. The specimen ends were polished on 600 metallographic paper and coated with Molykote for a lubricant. The compression rig consisted of an anvil resting on the machined table of the Baldwin Southwark testing machine and a plunger fixed to the movable cross

Jan 1, 1954

By d&apos, D. L. Guernsey, J. C. Entremont, John Chipman

The reaction of aluminum with oxygen in liquid iron has been studied at 1740° and 1910°C. Interaction coefficients are very much smaller than those previously published. The equilibrium constant falls within the approximate range of earlier experiments and calculations. It is now well established that the "deoxidation constant" for aluminum in liquid steel at normal steelmaking temperatures is extremely srnall. Thus at 1600 the product [% Al] is of the order of 10- 14. At this temperature, therefore, great experimental difficulties are encountered in any attempt to obtain a direct measure of the constant. If the aluminum content of the metal is high enough to permit accurate analytical determination, that of the oxygen is too low. If the oxygen content is high, the aluminum is below the limits of detection. Our best values of the constant have come, therefore, from indirect calculations or by extrapolation downward from observations at higher temperatures.. For their studies in the range 1695° to 1866°C, Gokcen and chipman' restricted their aluminum concentrations to less than 0.06 pct. Oxygen analyses were made by the vacuum fusion method which appears to be dependable at these low aluminum concentrations. Experimental results, even at the highest temperature employed, are extremely sensitive to small errors in the analysis of either element. The slight change in the equilibrium constant with aluminum and oxygen concentration was utilized in the calculation of interaction coefficients expressing the effect of aluminum on the activity coefficient of oxygen and the reciprocal effect of oxygen on the activity coefficient of aluminum. The range of concentration, however, was so limited that only a rough value for the interaction coefficient could be obtained. This value was much more negative than that found for any other pair of reactants. In view of the very limited range of concentration employed, the reported values have always been regarded as very questionable. A redetermination was the object of the work reported here. EXPERIMENTAL METHOD At high aluminum concentrations, the vacuum fusion method is susceptible to grave error due to absorption of gas by aluminum distilled from the sample. Since it was desirable to extend the study to at least as much as 1 pct Al, another method for analysis was sought. In steels containing more than a few hundredths of a percent aluminum and no other deoxidizing element, it is safe to assume that

Jan 1, 1963

By Nathaniel Arbiter, Arthur F. Taggart

THE chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 c.c. of a solution containing 495 mg. of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative proof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type [R+ + Y- + MX =± RX + M+ + Y¬] where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the massaction and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or Y-. Experimental work comprised determination of (1) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (2) the contact angles1 of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run with barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1944

By R. I. Jaffee, H. R. Ogden

AT the present time, there appear to be two conflicting opinions on the solubility of boron in titanium. P. Ehrlich' has indicated from X-ray diffraction work that boron is soluble in titanium up to TiB0.8 (17.8 wt pct, 44 atomic pct). The X-ray diffraction pattern for titanium was found in compositions up to TiB0.05_0.07 (1.1 to 1.6 wt pct); then, without a phase gap, superlattice lines appeared up to TiB0.8 On the other hand, Craighead, Simmons, and Eastwood' have estimated the solubility of boron in both alpha and beta titanium to be less than 0.1 wt pct, based on results of metallographic analysis. In some recent work done at Battelle, results were obtained which shed more light on the titanium-rich end of the titanium-boron system. Iodide-type titanium and high-purity crystalline boron were used in this investigation. The boron was prepared by hydrogen reduction of boron tri-bromide and deposition on a hot tungsten wire. The alloys were prepared by arc melting in an argon atmosphere of 10 cm Hg pressure on a water-cooled copper hearth. The ingots were hot rolled to strip at 850°C. Alloys containing up to 1 pct B could be hot rolled. Those containing 2 pct or more B could not be hot rolled. Metallographically, it was found that a second phase was present in alloys containing as little as 0.4 pct B, and that the quantity of second phase increased with increasing boron content. This is illustrated in Figs. la and lb, which show the microstructures of a Ti-0.4B and a Ti-1B alloy annealed in argon at 850°C. X-ray diffraction patterns of alloys containing 1 and 5 pct B revealed the presence of extra lines which correspond to the superlattice lines reported by Ehrlich.' However, no evidence was found of a shift in the lattice constants of alpha titanium indicating that there is very little, if any, solubility of boron in alpha titanium. This fact, coupled with the fact that the alloys were definitely two-phase, indicates that the extra lines are not superlattice lines, but are more probably the result of a second phase of a hexagonal structure almost identical in cell

Jan 1, 1952

By Maxwell Adams

OLIVER C. RALSTON, Salt Lake City, Utah.-We are indebted to these two gentlemen for the work which they have done with the oils derived from sage brush. Their work should not be confused, however, as the work of Mr. Adams deals with steam-distilled oils and that of Mr. Clevenger with destructively distilled oil, largely. In other words, Mr. Adams' oil is probably the original essential oil that existed' in the brush before distillation while Mr. Clevenger's oil not only contained this essential oil but also some products of destructive distillation of the wood constituents. I had noticed the work of Mr. Adams on attempting to separate the various constituents in the oils of some of the Western conifers and had sent to him to ask if he could send me small samples of some of. these pure products. This he very kindly did, and with them included some samples of oil from the common sage brush, whose characteristics he has here described, as well as a sample of oil from the common "rabbit brush." Only the sage brush oil proved of much value for flotation, but it, was very powerful, and I so informed Mr. Adams. Even in amounts as small or smaller than 1/10 lb. per ton of ore, it gave very quick and positive flotation of many ores, with high-grade concentrates and good extractions. It proved to be especially desirable for the flotation of carbonates of lead and of copper which had received an artificial coating of sulphide by treatment with a solution of a soluble sulphide. I also received a sample of crude pyroligneous acid from sage brush prepared by Dr. W. C. Ebaugh, of Salt Lake City. It did not do very good work in flotation, but it is possible that by concentration of this product to obtain the residual tar a good flotation oil might result. This has not been done as yet and I am sorry to see that Mr. Clevenger has not done this. It might be that the dissolved tar, added to the settled tar, would make a total yield of flotation oil higher than the 4 per cent. which Mr. Clevenger feels is a safe estimate. The importance of this point will be seen in the following discussion of the possible costs of sage brush oils for flotation.

Jan 10, 1916

By A. F. Taggart, Nathaniel Arbiter

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles' of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By Nathaniel Arbiter, A. F. Taggart

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles' of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By R. B. G. Yeo

The effects of alloy additions on the M, and A, temperatures of an Fe-22.5 pct Ni alloy have been determined. Increasing amounts of titanium, colum-bium, vanadium, and silicon raise and then lower M,while raising A, cmtinuously. Cobalt raises both M, and A,. Aluminum has little effect on Ms but raises A,. Chromium md nickel lower M, and A,. It is proposed that elements raise M, in accordance with their effect on the Ae3 temperature of iron until the lattice becomes stiffened against the shear transformation so that M, is then lowered. An anomaly, first pointed out by Zener,1 arises in steels when the addition of elements, such as molybdenum and tungsten, which raise the Ae3 temperature, also lower the M, temperature.2'3 During the development of a series of martensitic precipitation-hardening (maraging) steels, the effect of several elements on the transformation of austenite to martensite was studied. The results show that under suitable conditions several elements which raise Ae3 also raise the M, and A, temperatures. PREPARATION OF MATERIALS STUDIED A series of alloys was made in which cobalt, titanium, columbium, vanadium, silicon, aluminum, molybdenum, chromium, and nickel were added to an iron base containing 22.5 pct Ni. The compositions of the alloys prepared are given in Table I. The residual manganese contents of the heats were in the range of 0.030 to 0.35 pct, silicon 0.05 to 0.1 pct, carbon 0.0008 to 0.009 pct, and nitrogen from 0 to 0.004 uct. The allois were made as 50-lb induction heats starting with electro-iron and electro-nickel, melted in air to oxidize impurities. Additions of silico-manganese and ferro-silicon were made after which the power was turned off to allow the products of deoxidation to rise and be skimmed from the surface of the melt. The furnace chamber was pumped down to a pressure of 5 p and the charge was heated to 2900°F for the addition of other alloying elements. The heats were poured into five 10-lb ingots, making successive alloy additions to each. The ingots were soaked for 2 hr at 2300°F and hot-worked to 3/4-in.-diam bars. This stock was heated to 1500°F for 1

Jan 1, 1963

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.' This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,' a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By H. E. Doerr

The writer has been unable to find much information relative to tests made to determine the effect of forging on the specific density of steel. The opinion, however, among men engaged in the business, seems to be that forging greatly compresses or consolidates the steel. While such is doubtless the case with spongy or porous steel, the following experiments indicate that there can be little or no change in the density with steel initially free from cavities. Ten ingots of basic open-hearth steel cast as shown in Fig. 1 were used in the experiments. All the specimens were 0.53 carbon with all other elements the same, the analysis being determined from drillings taken midway between the center and outside of the upper end, as shown in Fig. 2. The specimens were selected from over one thousand ingots so that the tests could be comparative for the work done in forging only, but no two of the ingots were cast in the same heat. Each ingot remained in the mold approximately 30 min., when it was removed and sir-cooled. About 12 hr. later, when the temperature had been reduced to approximately that of the surrounding atmosphere, the head was discarded and the ingot heated in an oil furnace to approximately 2250" F. (1235" C). Approximately 1 min. was required to forge under the steam hammer to 1 1/4 in. (31.75 mm.), rough diameter, as shown by the dotted lines in Fig. 2. All ingots were allowed to air-cool after forging. Cylinders 1/2 in. (17.7 mm.) in diameter and 1/2 in. high were then turned from the forged and unforged parts of the ingots and numbered. The ten pairs of specimens were submitted to Louis E. Endsley, Professor of Railway Mechanical Engineering, University of Pittsburgh; A. N. Talbot, Professor of Applied Mechanics, University of Illinois; L. Z. Slater, chief chemist, Scullin Steel Co., St. Louis, Mo. NO information was furnished as to which specimens were forged or unforged and each laboratory used the same specimens, submitting the average of three independent determinations, a tabulation of which is shown in the accompanying table in which the laboratories are designated by the letters A, B, and C. While there is considerable difference in the individual determinations for a number of the specimens, the averages

Jan 1, 1920

National Minerals Advisory Council A meeting of the National Minerals Advisory Council on August 3rd in Washington, D. C., indicated the vitally important part that the mining industry is to play in the mobilization program. Director James Boyd of the Bureau of Mines told the Council that the Department of the Interior would review the recommendations of all the Council's commodity committees with regard for mobilization planning in the light of the changed international picture. The Council was requested to reactivate its commodity committees and have them gather all available data on supplies, their sources and availability and present and potential production of the minerals and metals represented on each committee. Data on labor, machinery, transportation, automotive and stationary equipment, power, fuel, lumber, water supply are a few of the important items called for in the reports, which are to be presented at a meeting of the Council on September 1 at Salt Lake City. The material in the reports will become the basis for discussing metal and mineral requirements at that time. Discussion at the meeting bared several $64 questions, probably the most important of which are the following: 1. Which of the war-essential metals and minerals and in what quantities can we reasonably expect to get them from abroad under threat of submarines? 2. How are we going to meet the manpower problem posed by (a) migration of labor from mining to manufacturing since the end of World War II and (b) the draft and the calling up of reservists? Opinion was expressed by industry spokesman at the meeting that the function of complying with mobilization requirements be left to those in the industry itself; that is, those having the "know how." This view contended that any administrating governmental agency should be kept as small and streamlined as possible. There was general sentiment against the reactivation of the wartime Premium Price Plan or other bonus plans as a stimulus to production. The thought was emphasized that what was needed was a change in the basic conditions which have fostered the decline in domestic mining activity in the postwar years. One such condition, long overdue for correction, is the tax structure as it applies to mining enterprises. Many quarters both in industry and in government favor tax relief along the lines suggested in the six tax recommendations by the Council to the Secretary of the Interior last December. The Council adopted a resolution expressing a feeling that the following tax recommendations are still feasible and desirable and will accomplish as much toward increasing exploration for new deposits (thereby subsequently increasing production) as will government loans for exploration: (1) Losses from unprofitable ventures should be allowed corporations, partnerships, or individuals as ordinary deduction against current income. (2) Development costs after discovery should be recognized as operating expenses. (3) Allowance for depletion should be made to the stockholder as well as to the corporation. (4) Income should not be taxed without full allowance for losses of loss years. (5) Adequate allowances for percentage depletion should be made. A discussion of the manpower problem led to the Council's acceptance of a resolution advising that "military authorities should proceed with caution in depriving the mining and metallurgical industry of its manpower." The resolution strongly urged that no personnel "directly engaged in exploration, development, production or supervision (of strategic and critical materials) should be drafted for the armed forces, at least until the anticipated demands upon these producers are clarified." Stockpiles The Munitions Board's "Stockpile Report to the Congress" of July 23, 1950 revealed: (1) The total estimated value of the stockpile objective is $4,051,714,510 at the close of fiscal year 1950. (2) The total value of the stockpile on hand, at the close of fiscal 1950 was $1,556,154,352 or 38.4 pct of the total stockpile objective. An additional $494,948,060 was on order, making a total of 50.6 pct on hand plus the amount on order. (3) Materials obtained for the stockpile by the ECA from January to June 1950 amounted to $13,112,085, while development projects by ECA during this period involved the expenditure of $9,322,000, mainly with counterpart funds. Shortly after the start of the Korean conflict it was felt that Congress ould appropriate greatly increased sums for the purchase of materials for the stockpile. This stimulus to the program may increase the dollar earnings of those European nations that are present or potential contractors in our stockpiling program. Such a development would mean that these nations could add to their gold reserves, thereby stabilizing their respective economies and hastening recovery. This seems to be the picture for the next six months anyway. The "bug" appears when it is realized that the increased threat of total world war actually may retard recovery in Europe as nations on the continent may feel inclined to devote more of their resources to defense programs. Industries Essential to Defense The Department of Commerce in response to a request by the Department of Defense issued on August 3, 1950 a "Tentative List of Essential Activities" as a "guide for calling up for active duty members of the civilian components of the Armed Forces." The list includes the following: Primary Metal Industries. Included herein are establishments engaged in the smelting and refining of ferrous and nonferrous metals from ore, pig, or scrap. Metal Mining. This category includes establishments primarily engaged in mining, developing mines or exploring for metallic minerals (ores). This group includes all ore dressing and beneficiating operations. Anthracite Mining, Bituminous Coal and Lignite Mining, Crude Petroleum and Natural Gas Extraction, Mining and Quarrying of Nonmetallic Minerals, Except Fuels. Challenge to the Mining Industry The source of our country's great strength lies in its capacity to produce. In times of stress such things as national morale and manpower are all-important but without a capable industrial machine we would be helpless. That machine must be fed with minerals and metals in order to generate and maintain momentum sufficient to insure success. Consequences of the lack of adequate supplies of essential metals and minerals to increase and sustain our industrial power are not pleasant to contemplate. It is absolutely imperative that we put forth Herculean effort to guarantee ample supplies of such essential materials as copper, lead, zinc, manganese, antimony, mercury, tungsten, tin, chromite, nickel, cobalt, iron ore and rubber. The mining industry faces a challenge more serious than ever existed before in the history of our country. The industry must be equal to the task.

Jan 9, 1950

By F. L. Toy, C. E. Sims

I. A. Sirel—I would like to ask Mr. Sims what would the preferred hot metal analysis be as far as manganese and silicon are concerned if you used specially made iron for this process instead of basic iron. C. E. Sims (authors' reply)—A preferred composition would contain somewhat less silicon than the basic pig iron used in these experiments. High silicon requires a large lime addition. Lime must be added in sufficient quantity to neutralize the silica formed and to leave an excess for dephosphorization. Manganese presents almost no problem in operation. It is almost completely oxidized and, in burning, develops considerable heat. The evidence indicates, however, that, in continuous commercial operation, there will be an excess of heat produced, and the bath will need to be cooled in some manner as by the addition of scrap or by utilizing the energy for the direct reduction of ore. There do not seem to be any serious limitations on composition of pig iron. One heat was made with an iron containing 2.27 pct silicon and the phosphorus finished at 0.007 pct. In another, the iron contained 0.45 pct phosphorus which was lowered to 0.019 pct. This indicates considerable leeway in composition. D. R. Loughrey—We are all very much interested in the recent discovery of very large deposits of iron ore both in Labrador and in Venezuela. I would like to ask Mr. Sims if the iron ore at either or both of these places is such that it would lend itself to the manufacture of iron suitable for use in the turbohearth. C. E. Sims-—According to my information, those ores are not essentially different from ores now used in this country for making basic pig. They should, therefore, be adaptable to this process. D. I. Brown—You have spoken about the leeway, or spread in analysis of the various irons you can use in the vessel. I would like to have you tell us, if you can, about the different kinds of steels which can be made in such a vessel. The turbohearth process, or it might more aptly be called pneumatic openhearth, is a little different from that used in most Bessemer shops and in the one in which I worked. If we had a blow in the air over 10 min, the boss was in the pulpit in a hurry

Jan 1, 1951