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By M. Botz

For leach solutions containing primarily free cyanide, the silver nitrate titration method is a rapid and acceptably accurate means of analyzing for cyanide. However, in leach solutions containing elevated levels of copper, the titrimetric method significantly over-estimates the concentration of free cyanide and under-estimates the concentration of weak and dissociable (WAD) cyanide. The authors have developed a modified potentiometric titration method for determining WAD cyanide that overcomes issues with high copper levels in solution. The new MP-WAD method involves addition of a chemical ligand to the sample prior to silver nitrate titration to fully release cyanide bound to copper. Once released from copper, cyanide in solution is no longer affected by the presence of copper and titration results are quantitative rather than empirical. In multiple laboratory trials with synthetic solutions and complex actual leach solutions, accurate WAD cyanide measurements were achieved using the MP-WAD method. Analyses obtained with the new method were found to be within about ±10% of analyses obtained with the USEPA OIA-1677 WAD cyanide analytical method.

Feb 27, 2013

A flow sheet has been developed to treat a high tonnage highly preg-robbing gold ore. The ore is low grade and fine grained with a high proportion of very fi ne free gold. The key components of the flow sheet include gravity, flotation, intensive cyanidation with direct electrowinning, and carbon-in-leach of the flotation concentrate. The circuit produces a low overall mass pull to concentrate allowing economic intensive treatment of large tonnage low-grade material. Efficient recovery of fine gravity gold using a Falcon concentrator in both the milling and flotation circuits, and subsequent intensive cyanidation in a Gekko InLine Leach Reactor (ILR) is critical to the process with over 70 per cent gold recovery expected in this circuit. Grind size control was also found to be important in controlling the activity of the preg-robbers in the carbon in leach circuit and also in the solid liquid separation performance. Tests at the large-scale demonstration plant have been conducted to demonstrate the effectiveness of this flow sheet. A large low-grade deposit is currently under development with the aim of developing a 10 Mt/a treatment plant with the subsequent addition of equivalent sized process lines in multiples of 10 Mt/a. The economic development of this orebody is critically dependant on understanding and exploiting the properties of the ore. In particular it is critical to minimise the effect of preg-robbers by recovering free gold with Falcon concentrators and InLine Leach Reactors. Recovery of the remaining gold by flotation into a small mass yield allows this fraction of gold to be treated by CIL leaching utilising high carbon levels. It is critical is to ensure operation at the optimal grind size to maximise liberation of the free gold and minimise pregrobber activity. The ore has been identified as preg-robbing with low recoveries obtained if treated using conventional cyanidation and carbon absorption. The mineralogy consists of predominantly fi ne grained free gold with minor sulfides including pyrite and arsenopyrite. With conventional cyanide leaching in the absence of carbon, gold recovery is less than 50 per cent. Direct cyanide leaching of the ore in the presence of activated carbon results in an improved but still uneconomic gold recovery. The gravity recoverable gold (GRG - as defined by Andre La Plante) content of the ore has been measured to be 70 per cent to 85 per cent in various tests with liberation grind size of approximately 106 ¦m. This indicates gold is predominantly free and suitable for recovery by batch centrifugal concentrators into a low mass yield. This property of the ore presents the opportunity to maximise the recovery of gold by separating it from the majority of the preg-robbers prior to leaching. Due to the very fine gold particle sizes and the necessity to maximise recovery of this fine fraction Falcon concentrators were selected for the duty, with their proven high recoveries at very fine gold sizes. The gravity recovery in the milling circuit is designed to be in the range 55 to 65 per cent. This has been achieved in the existing pilot plant using a Falcon operating on ball mill discharge within the mill recirculating load. Intensive leaching in an InLine Leach Reactor is essential to recover the gold from the gravity concentrates. Tabling is not a preferred option since recovery is lower than intensive cyanidation and any gold losses to table tails will report to CIL where recovery is reduced by the presence of preg-robbers. Furthermore, tabling recovery from the gravity concentrates is particularly poor due to the fine particle size of the free gold. ILR recoveries of 98 per cent were demonstrated in the pilot plant using an ILR100BA and leach conditions were investigated in the lab using pilot plant generated Falcon concentrate. Recovery of gold from the pregnant solution was achieved with direct electrowinning at pilot and efficiency and sizing parameters were determined at lab scale. To further increase free gold recovery Falcon concentrators will be installed in the flotation circuit. Location of the Falcons in the circuit is not finalised but installation on the rougher concentrate stream is favoured since it will allow multiple pass recovery. This is expected to recovery a further ten to 20 per cent of the gold, as indicated by lab tests on pilot plant generated material. The gravity concentrate from the flotation circuit will also be leached using InLine Leach Reactors. Initial intensive cyanidation tests carried out on lab generated flotation concentrates indicated higher recoveries than CIL can be obtained even though the concentrates contain significant levels of preg-robbing material. This can be explained by the high cyanide, high pH leaching conditions used in the ILR which alters the absorption equilibrium of the preg-robbers. Further optimisation of the leach conditions will be undertaken once more concentrate becomes available. Recovery of the remaining gold content is achieved by flotation into a small mass yield, however the preg-robbers are also recovered into this concentrate. Due to the presence of the preg-robbers gold leaching must be carried out in the presence of high levels of activated carbon in a CIL system. The recovery has been shown to be strongly dependant on the carbon loading and the concentrate particle size. The carbon competes against the preg-robbers for dissolved gold while excessive grinding increases the surface area and activity of the preg-robbers. This has been demonstrated in test work however the economic optimum leaching conditions and carbon loading have yet to be determined. The grind size is critical to the economics of the project, not only due to its effect on gold recovery but also due to its effect on the major operating and capital costs at both the front and back end of the process. It is critical to grind enough to obtain both gravity free gold and flotation liberation at low mass yields however over-grinding results in large increases in mill size and power at the front end and filtration or thickening costs at the tails. Because these unit operations treat essentially all the plant feed even small changes can result in major impacts on project economics. The viability of this project is greatly enhanced by the high recovery of gold into a small mass yield. In particular the production and intensive leaching of the free gold gravity concentrates will allow over 70 per cent of the gold to be recovered efficiently with minimal impact from preg-robbers. By using flotation the mass of the remaining fine preg-robber contaminated material, to be leached in CIL, is greatly reduced allowing this difficult material to be economically treated. This is an ABSTRACT ONLY. No paper was prepared for this presentation. 

Aug 1, 2010

By H. Sarvamangala

Biomineralization of manganese on titanium condenser material exposed to seawater has been illustrated. Biom-ineralization occurs when the fouling components, namely, the microbes, are able to oxidize minerals present in water and deposit them as insoluble oxides on biofilm surfaces. Extensive biofilm characterization studies showed that an alarmingly large number of bacteria in these biofilms are capable of oxidizing manganese and are, thereby, capable of causing biomineralization on the condenser material exposed to seawater. This paper addresses studies on understanding the exact role of the microbes in bringing about oxidation of manganese. The kinetics of manganese oxidation by marine Gram-positive manganese oxidizing bacterium Bacillus spp. that was isolated from the titanium surface was studied in detail. Manganese oxidation in the presence of Bacil-lus cells, by cell free extract (CFE) and heat-treated cell free extract was also studied. The study confirmed that bacteria mediate manganese oxidation and lead to the formation of biogenic oxides of MnO2, eventually leading to biomineralization on titanium surface exposed to seawater.

Jan 1, 2008

By Stephen Hammond

?Our own prejudices form the greatest barrier to creating an inclusive working environment.? Have you witnessed? Racism or Negative Comments about an Aboriginal Person? ?You are free to compete with all the others?, and still justly believe that you have been completely fair.? Lyndon B. Johnson

May 1, 2008

By Harold B. Treweek

The development of full scale flotation circuits based on laboratory and/or pilot plant data is discussed. Auxilliary operations, equipment and layout essential for trouble-free start-up and operation are noted. The selection of flotation cell size is discussed as it affects plant capital and operation costs.

Jan 1, 1978

By Jr. Arcand

Canadian Economy ? Getting Results ???? A stronger Canadian economy ???? National debt cut ???? Taxes reduced, tax-free savings account, support for manufacturing sector ???? Assisting with infrastructure Aboriginal issues affect all Canadians ???? Aboriginal prosperity is in everyone?s interest ???? Conditions for Aboriginal success include: - Indian residential school settlement - resolving outstanding specific claims

May 1, 2008

By Nikolaos Petropoulos, Ulf Nyberg, Daniel Johansson

A series of signature boreholes were blasted to observe any difference between confined and free face blasts. Four geophones were used to capture the compressive wave. The conventional approach, i.e. the calculation of vectorized peak particle velocity (vPPV) did not show any difference. Also a wavelet transform was tested.

Feb 1, 2020

By Larry B. Fiske

Elimination of dust and processing of fines for both thermal and metallurgical coals is addressed. The efficiency of treatment with lignosulfonates compares favorably to oil in thermal coal. Effect of treatment with various lignosulfonates upon cokability of metallurgical coal was determined by Free Swelling Index, Gieseler Plasticity and Arnu Dilatation.

Jan 1, 1992

By J. J. Geraghty

U.S. Bureau of Mines researchers investigated the development of an innovative transport system for underground coal mining. A one-half commercial-scale bench model was constructed. Novel magnetic levitation (mag-lev) technology was developed. Frictionless and contact-free transport of a prototype materials container and payload has been demonstrated.

Jan 1, 2010

By Ramin Motamed, Farshid Ghazavi, Joseph A. W. Toth

"Post-disaster reconnaissance of areas affected by earthquakes has documented extensive damage to buildings with shallow foundations located in liquefaction-prone areas. Currently, estimation of liquefaction settlement is based on empirical correlations that evaluate settlement in the free-field environment and are based on one-dimensional consolidation. However, observations have shown that liquefaction settlement under buildings can be considerably greater. This research is based on a series of 1- g shake table experiments using a transparent soil box to reproduce liquefaction-induced building settlement. Building settlements were evaluated using a scaled model of a building foundation representing a 1-2 story building. Comprehensive parametric study was carried out to establish the effects of several parameters on free-field and building settlements such as building width and thickness of liquefiable soil layer. The experiments utilized accelerometers and pore-water pressure sensors to monitor ground accelerations and buildup of pore-water pressures in both the free-field and model building footprint. Results of these experiments are compared to available centrifuge tests and field observations and conclusions are drawn with respect to the potential scaling effects. Lastly, this paper discusses the feasibility of installing helical piles as a mitigation strategy to reduce the building settlements by presenting some of the exploratory experimental data obtained from this series of 1-g shake table tests.INTRODUCTIONThe 2010-2011 Canterbury earthquake sequence and the 2011 Great Tohoku earthquake are some of the most recent examples where large numbers of low-story structures sustained damage resulting from liquefaction-induced settlements. This damage has commonly been observed in residential and commercial areas developed over loose, unconsolidated and saturated coarse grained soils resulting from both natural and man-made deposits. Damages incurred from the 2010-2011 Canterbury earthquake sequence occurred in the largely unconsolidated fluvial environment bordering the Avon River in Christchurch (Henderson 2013). Similar damage was also incurred during the 2011 Great Tohoku earthquake where liquefaction of soils occurred in both young alluvial deposits and fill materials (Ashford et al. 2011). Figure 1 presents typical modes of failure to structures resulting from the effects of liquefaction. Current practices in evaluation of liquefaction settlement rely on empirical correlations (Tokimatsu et al. 1987; Ishihara et al. 1992) developed for liquefiable soils in the freefield environment (Dashti et al. 2010a). However, recent observations of the performance of foundations suggest that settlement of rigid shallow foundations in liquefiable soils are commonly greater than those predicted in the free-field. Therefore, new correlations should be developed to better predict the degree of settlement of shallow foundations in liquefiable soils. Current research is beginning to focus on the mechanisms of settlement during liquefaction in regards to confining stress, pore-water pressure and shear stress induced from foundations (Dashti et al. 2010b)."

Jan 1, 2016

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author's reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By N. S. Dalal, V. Castranova, K. Van Dyke, V. Vallyathan, J. H. Kang

Previously we reported crushing or grinding crystalline silica results in silica-based free radicals on the particulate surface which can generate hydroxyl radicals in aqueous solution (1). Now we find that freshly ground silica is more cytotoxic to and a more potent activator of alveolar macrophages than similarly sized aged silica. Since the United States Department of Labor estimates that over 1.25 million American workers may be exposed to freshly ground crystalline silica arid nearly 60,000 may be at risk of developing some degree of silica-based occupational lung disease, then this is hardly a trivial problem. Occupations of concern include workers who come in contact with silica including miners of soft and hard minerals, stone quarry workers, glass workers and even millers who stone grind flour. Acute silicosis is manifested by inflammation, alveolar lipo-proteinosis, and the rapid development of respiratory disability that depending on the dose of silica can produce chronic silicosis which takes 20 - 40 years to develop. It is demonstrated by the appearance of concentric hyalinized nodular lesions and progressive development of dyspnea(3). Certainly the free radicals produced on the surface of freshly ground crystalline silica play a most important role in producing the acute and chronic symptoms of silicosis. When respirable-size freshly- ground silica (0.1 -- 5 microns in diameter) enters the deep alveolar spaces in the lung and contacts an aqueous environment, hydroxyl radical are generated and cellular damage is bound to occur. We have found that freshly ground silica can cause lipid peroxidation and lysis of erythrocytes(1). The objective of this investigation was to further elucidate the enhanced toxicity of freshly ground versus aged silica. It can be deduced from the data that not only is freshly ground silica more cytotoxic to alveolar macrophages but it is a more potent stimulant of these phagocytes. However the mere characterization of toxicity is not entirely helpful if there is not a useful means to detoxify the cause of the damage. We have identified an aqueously soluble substance that can be used in high dilution to detoxify the SiO(•) and Si(•) type of free radicals. This is the organosilane known as Prosil 28 (R). We have found that coating of the freshly ground silica can effectively reduce its toxicity. The importance of this observation is that such a coating could be used with water cooled drills. This may partially detoxify silica at the point of generation of the free radical, i.e., the generation of the fresh silica dust itself. Such a coating could be used in great dilution 1:103 or 1:104. The coating would be long lasting, inexpensive and should be non-toxic because of the great dilution.

Jan 1, 1991

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By A. A. Smith, J. S. Smart

NUMEROUS investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previously.1 The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range 0 to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synthesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature were obtained by drawing the continuous cast rod to wire of 0.081-in. diameter, employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By E. P. Abrahamson II

The effect of transitiorz element bitzary solid solution additions upon the recrystallization temperature of columbium has been investigated. The elements Mn, Fe, Co, Ni, W, Re, and 0s OWY the yecystallization tempel-aturye, while Ti, V, CY, zr, Mo, Ru, Rh, Pd, Hf, Ta, W, Ir, and Pt mise it. A correlation is kloted between the rate of chatzge of recyystallization tewaperature with atomic hercent solute and the free atom electron configuration of the solute element. The work of Abrahamson and Grant1 has indicated a correlation between the free atom ground-state electron configuration and the change in brittle-ductile transition temperature per atomic percent solute in chromium base alloys. A similar correlation was observed for the change in the recrystallization temperature of iron base alloys by Abrahamson and Blakeney and Abrahamson. It was also observed that the limit of rapid change in recrystallization temperature also Correlated with the electronic configuration of the free solute atom. A further study by Abrahamson4 established the generality of the phenomenon by yielding similar results for vanadium base dilute alloys. It has been inferred that a peri- odicity might be expected with changes in the free atom electron configuration of the solvent element. This study is the third set of transition base metal systems to be studied. It is the object of this and further studies on transitional metal systems to detect any systematic variations in the observed correlation which might contribute to the understanding of the electron interactions which are evidently exhibiting themselves. PROCEDURE All alloys were made using 99.9 pct Cb with 0.030 Ta, 0.016 0, 0.0025 H, 0.003 Mo, 0.021 Fe, 0.005 C, and 0.002 N. The solute elements were 99.9 pct pure. According to the published binary phase diagrams5 and metallographic examinations at X750, all additions were in solid solution. The alloys were arc melted and remelted 6 times in the form of cubic 400-g buttons under an argon atmosphere. They were then hot forged at 1200oC to 0.6-in. diameter, annealed for 3 hr at 1200o under argon, and furnace cooled. The specimens were then machined to 0.400 -in. diameter. Grain size was checked and found to remain essentially constant at 150 i 30 grains per sq mm. The specimens were then cold swaged to 0.187-in. diameter, yielding 46 i 1 pct cold work. All alloys were chemically analyzed for the major solute. Analyses of random samples indicated that the impurity content remained at the values of the starting material. Tungsten contamination was held to 0.007 pet.

Jan 1, 1962

By P. Chiotti, J. T. Mason

Metallographic, thermal, X-ray, and vapor-pressure data were employed in establishing the Ce-Zn phase diagram. Nine compounds and three eutectics were observed. The eutectic compositions in weight percent zinc and temperatures are 10 pct and 495"C, 37 pct and 795°C, and 56 pct and 810°C. Three of the compounds, CeZn, CeZnn, and CeZne.5, melt congru-ently at 825°, 87.505°, and 980°C, respectively; the other six compounds, CeZns, CeZns.67, CeZn4.5, CeZn5.25, CeZn,, and CeZnll, decompose peritectically at 820°, 840°, 870°, 885", 960°, and 795"C, respectively. The compound CeZn5.25 is an AB5 type with a small range of composition which lies on the zinc-rich side of the 1 to 5 stoichiometry. Zinc vapor-pressure data obtained by the dewpoint method were employed in calczilating the thermodynamic properties of both the liquid alloys and solid compounds. The data for the A critical review of the information available on the Ce-Zn system up to 1960 has been given by K. Gschneidner, Jr.' Of particular interest is the work by J. schramm2 who investigated the region between 55 and 100 wt pct Zn and reported a CeZn,, compound which decomposes peritectically at 785"C, a CeZn, compound which melts congruently at 972"C, and five temperature horizontals at 79@, 817", 840", liquid alloys were fitted to the relation from which the relation was obtained by integration. In these relations F XS is the excess partial molal free energy, N is atom fraction, and the constants c and d have the values c = (-22,000 + 7.0T) and d = 6171,000 + 74.0T). Relations for the standard free energy of formation for the solid compounds were derived from the data. At 973°K the enthalpy in kilocalories per gram-atom z)aries from —11.3 for CeZnz to —8.21 for CeZn~l and the free energy in the same units varies from —7.1 joy CeZn, to -3.82 for CeZn11. and 942°C in the region between 55 and 75 wt pct Zn. No attempt was made to identify other features of the system. I. Johnson and R. yonko3 used a fused-salt cell to measure the electromotive force between pure cerium and an alloy consisting of zinc-rich liquid in equilibrium with CeZnll. Solubility data for cerium in zinc has been reported by J. Knighton et u1 .4 Johnson and Yonko give the following equa-. tions for the mole fraction of cerium in zinc and the standard free energy of formation of CeZnll:

Jan 1, 1965