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By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By R. G. Davies

Above 500°C, where dislocation climb is rate controlling, it is observed that the activation energy for creep is independent of the apblied stress, although it varies from 62 kcal per mol at 15 pct A1 to 73 kcals per mol at 20 pctA1 due to the change in short-range ovdw with composition. Below 500°C, when the nonconservative motion of jogs upon dislocations is thought to be rate controlling, the activation energy is stress dependent. A sudden increase in the creep rate, for which no explanation is availab2e, occurs at the highest stress at all temperatures. CREEP has been the subject of numerous research publications during the past decade with most of the attention focused upon high temperature steady state creep, i.e., above 0.5 TM, where TM is the absolute melting temperature, as it is the most amenable to theory. Many of the proposed theories involve the climb of dislocations out of their slip plane, which allows them to circumvent obstacles or to annihilate dislocations of opposite sign on other slip planes.' For pure metals it is observed that the activation energy for this creep is equal to the activation energy for self diffusion.' The position is much more complicated in alloys as there are many possible microcreep mehanisms, as well as dislocation climb, which could be rate controlling. There has been little systematic investi- gation of alloys, but Weertman (lead and indium base alloys)3 and Lawley, Coll, and Cahn (Fe-A1 alloys)4 suggest a microcreep process as the controlling factor. A Cottrell-Jaswon atmosphere mechanism is proposed for the lead and indium alloys, and a mechanism involving crystallographic order for the Fe-A1 alloys. Lawley et al. showed that the formation of a super-lattice, either of the FeAl or Fe3A1 type. decreased the rate and increased the activation energy for creep. From the measurements of lattice parameters,= resistivity,' magnetic properties,7'8 internal friction: and dilatometry10 the ordered region is thought to commence at -19 at. pct Al. However, a recent investigation by the author indicates a value

Jan 1, 1963

By H. W. Kilau

Thermodynamic calculations indicate that an electrochemical cell might serve as an analytical device for determining the composition of high-purity metals. An equation, readily derived, for the cell voltage, E, is as follows: [E I RT In F NFe unknown sample T of L NFe standard] The cell, however, must come to equilibrium, must be reversible, and must have no thermal effects or complicating side reactions whose magnitude is indeterminable. This Bureau of Mines investigation explores the feasibility of an electrochemical technique for the analysis of high-purity iron. Experiments were conducted using room-temperature aqueous cells and high-temperature molten salt cells. The room-temperature cells proved to be irreversible. The high-temperature cells utilizing FeCl2 and a eutectic mixture of KC1-LiCl were reversible, but did not attain a constant voltage necessary for analytical considerations.

Jan 1, 1963

By Robert S. Warfield

The Bureau of Mines investigated a geologically favorable area in the Beluga River coalfield in south-central Alaska to determine if there were sufficient minable coal reserves for onsite utilization to meet the projected thermal power needs of the Anchorage area. A program of diamond core drilling and sampling delimited a shallow saucerlike structure estimated to contain indicated reserves of more than 20 million tons of subbitminous coal in a seam over 50 feet thick that could be mined by opencut methods. A large sample of fresh coal was taken across the full width of the seam for washability studies. This sample, with 4 volume-percent of clay partings eliminated, contained 24.4 percent moisture and 16.8 percent ash and had a calorific value of 7,162 Btu per pound. The studies indicated that mechanical cleaning would be of doubtful value.

Jan 1, 1963

By Tanner A. C, Harraway D. H

Various circuits were tried at Mount Isa Mines during the period 1959 to 19G3 with the objective of improving the differential flotation of galena and sphalerite. Many benefits and disadvantages of the various circuits were revealed. An analysis' of ore characteristics and their effect on flotation was made -and resullted in the design of a proposed circuit which is currently in the process of installation.INTRODUCTIONSince 1936 when lead-zinc sulphide flotation commenced at Mount Isa, at least three types of ore have been encountered.Each ore has presented problems to flotation metallurgists.The three types of ore are,1. partially oxidized upper level sulphide ore,2. Black Star ore from the lower levels with its carbonaceous fraction, and3. Black Rock ore which is similar to 2, but more free milling.In retrospect a number of the metallurgical successes of the past were short lived. Often flowsheets or 0perating practices were designed to solve a single metallurgical problem associated with the current ore being treated. As the ore changed the problem would vanish and the method originally taken to counter the problem could become unnecessary or deleterious to the treatment of the new ore. The general lesson learnt from-the past-is-that thetreatment of Mount Isa lead-zinc ore involves a number of equally major problems...

Jan 1, 1963

By G. L. Alston

Rigid urethane foam can be used effectively for improving mine air conditioning systems by reducing heat and moisture transfer from mine rock to ventilating air and from mine rock to ventilation ducts, for erecting mine ventilation stoppings and overcasts, for sealings around door frames and bulkheads to prevent air leakage, for preventing spalling and sloughing of roof and rib and for erecting fire-resistant powder magazines and transformer or compression stations. Rigid urethane foam is a tough, cellular material, made by nixing diisocyanate and polyether polyol resin in accurate proportions through an applicator system, then the two chemicals react, the mixture expands thirty times its original volume with 85 to 95 percent closed cells. Within seconds, the mixture solidifies and takes a preset which will adhere to overhead or vertical surfaces. It will adhere to brattice cloth, steel, wood, concrete and rock, Excessive wetness will reduce the adherence, but in such cases adherence can be improved by preliminary application of an absorbent dust such as cement.

Jan 1, 1963

By E. Maré

Some of the members will probably ask themselves what close relationship exists between hydro-metallurgy and a wet scrubber, but we are sure that as soon as deeper thought is given to the matter it will be realised how vital scrubbing, operations are in metallurgical plants. In ordinary metallurgical installations or pyro-metallurgical processes ore concentrates are first of all shifted from place to place and dust is created. In other cases the ores or concentrates are crushed or dried or roasted, and in each one of these operations dust and fumes, are created. All suspended particles and fumes originating from the abovementioned conditions not only, in many instances, provide health hazards which disrupt production and endanger the personnel in the plant, but also are the source of economic losses through extra maintenance and wear to moving machinery due to abrasion and corrosion. Further losses are incurred by the waste of fine, very often valuable, components. The Party who once said that in several metallurgical plants the bulk of the profits was discharged into the atmosphere by the stack wasn't stretching the truth. There is a place in Africa where a gold producing concern used to lose over 5 oz. of fine gold per day out of a total production of 3000 oz. per month. In another instance, copper concentrate going as high as 80% Cu was discharged into the atmosphere at the rate of 4 tons per day. Realising the value of removing and collecting solids and fumes created in metallurgical plants, a thorough study was made of the available plant and equipment offered on the market. Some units were found very efficient, but very expensive; some others also very efficient but with temperature and maintenance limitations. Some others were also efficient but prohibitive from the point of running costs.

Jan 1, 1963

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Experimental results are given for the rate of reduction of silica from silicate melts by paphite-saturated iron in the presence of carbon monoxide. It is shown that, when gas bubbles are present at the slag-metal interface, the interfacial chemical reaction is the rate-controlling process in the transfer of silicon from slag to metal. From the silicon-concentration profiles in the metal sample, the diffusivity of silicon in paphite-saturated iron is found to be (5.4 * 0.4) x 10 sq cm per sec at 1600°C. Some consideration is given to the transport of oxygen from the slug-metal interface to the walls of the gvaphite metal container as becoming the rate-controlling process in the absence of gas bubbles at the slag-metal interface. ATTEMPTS were made by Fulton and chipman1 to investigate the kinetics of reduction of silica from calcium alumino-silicate melts by graphite-saturated iron in an atmosphere of carbon monoxide. In these experiments with 400 to 500 g of metal and slag, both phases were stirred in such a manner that the interface was essentially undisturbed. Initially, the graphite-saturated iron contained about 15 pct Si and, after about 8 or 10 hr of reaction time at 1600°C, the silicon content of the metal in- creased by about 0.2 pct. In a written discussion on this paper of Fulton and Chipman, schuhmann2 pointed out the possibility that this observed slowness of the reduction of silica could be due to the transport of oxygen across the liquid metal boundary layer at the slag-metal interface. Although this explanation of Schuhmann is quite feasible for the experimental data of Fulton and Chipman on silica reduction, such a reasoning should not be extended to other rate data on slag-metal reactions unless sufficient evidence is available satisfying the boundary conditions for such a transport process. The hydrodynamics of stirred liquids are very complex and even for a simple method of stirring there is no exact mathematical solution which will predict the mass transfer coefficient accurately. The best available solution of this problem is that given by Lewis' and later modified by mayers~ for a two-liquid system where liquids are stirred by counter-rotating stirrer blades without disturbing the interface. In such a system the mass transfer coefficient is estimated from an empirical relationship using the data on viscosity and density of the two liquids, rate of revolution, the length of stirrer blades, and the diffusivity of the element which is transferred from one phase to the other. It was found in these investigations' that the estimated and observed mass transfer coefficients, in systems containing two immiscible aqueous solutions, agreed within *40 pct. Although this is not considered to be an unreasonable error for the study of industrial processes, uncertainties of this magnitude cannot be tolerated in any theoretical study of reaction kinetics. In view of the complexity of the

Jan 1, 1963

By W. J. Boone

Experimental determinations were made of vapor-liquid equilibria data for a helium-nitrogen-methane system. A mixture composition was chosen to approximate the crude helium to be produced Or conservation that will eventually be further refined to obtain pure helium. Although there are publications of studies of the vapor-liquid equilibria of helium-nitrogen, helium-methane, and nitrogen-methane binary systems, there is little indication of work done on the ternary system of helium-nitrogen-methane. The experimental data presented in this report supplement the information available for the binary systems. The equilibrium vapor-liquid data and equilibrium vaporization coefficients are presented in tabular form. Graphs are employed to show an extensive amount of the data.

Jan 1, 1963

By R. H. Richman, II Conard G. P.

AS part of a study of deformation twinning in bcc crystals, solid solutions of beryllium in iron have been found to twin profusely when strained slowly at room temperature. This note reports some crystal-lographic aspects of the operative mechanical twin modes in a quenched Fe-5 wt pct Be alloy. After melting twice under a partial pressure of helium, the alloy was homogenized, cut into pieces 7 to 10 mm on an edge, solution treated at 1130°C,1 and quenched. Debye-Scherrer patterns confirmed

Jan 1, 1963

By W G. Brese

The attention of the world is being focused on the spectacular rise of elemental sulphur production in Alberta. In the short space of a decade, production has increased from less than 10,000 long tons, in 1952, to al-most 1,000,000 long tons in 1962. Moreover, 1963 sulphur production is expected to rise by 50 per cent to approximately 1,500,000 long tons, and further increases are forecast for ensuing years. The reason for this dramatic in-crease in elemental sulphur production, particularly in the last year or two, is that Alberta elemental sulphur is recovered in association with the production of sour natural gas. When very large volumes of natural gas began moving to U.S. markets in the latter part of 1961, the resultant increase in sour gas production led to a marked increase in the production of sulphur. Consequently, Canada, mainly on the strength of sulphur produced in Alberta, will soon become the second largest producer of sulphur in the Free World

Jan 1, 1963

By John Plecash

This paper comprises a general outline of all of the developments, including the history, geology, mining, milling, power and transportation installations, at the gold mining operation of La Luz Mines Limited and the copper mining operation of its wholly-owned subsidiary, Rosita Mines Limited, both located in north-central Nicaragua. The low-grade, gold-bearing ore-bodies of La Luz Mines, contained in highly fractured and folded Lower Cretaceous sedimentary rocks, were from 1909 to 1928, mined and treated by primitive methods by the La Luz and Los Angeles Mining Company. The abandoned property was acquired by La Luz Mines Limited in 1936, and was equipped with modern machinery and put into production in 1939. Between 1939 and 1948, the daily rate of production was in-creased from 300 tons per day to 2,-000 ton per day. The ore reserves available for open-pit mining were depleted in 1954. Since then, the entire production has come from under-ground operations.

Jan 1, 1963

By G. W. Birge

Carbonizing properties of the principal coalbeds of Elk, Clarion, Jefferson, Clearfield, and Centre Counties, Pa,, are described in this Bureau of Mines report, Twenty-six samples, representing the Upper Freeport, Lower Freeport, Upper Kittanning, Middle Kittanning, Lower Kittanning, and Brookville beds, were carbonized by the Bureau of Mines--American Gas Association (BM-AM) method, and yields of products and physical properties of cokes were determined. Expansion or contraction of the majority of the samples was measured in the Bureau of Mines sole-heated oven. Chemical analyses, agglutinating values, and free-swelling indexes are given for all samples. In this area the coals generally are characterized by high sulfur and moderately high ash content, and their suitability for metallurgical use would depend largely upon satisfactory cleaning. The samples from Elk, Clarion, and Jefferson Counties were high-volatile A bituminous In rank, whereas, most samples from Clearfield County and all those from Centre County were of medium-volatile rank. Coals from Clarion County had dry, mineral- matter-free fixed-carbon contents ranging from 56.5 to 60.3 percent and were weakly coking. With the exception of two samples which contained excessive ash, the medium-volatile coals of Clearfield and Centre Counties were strongly coking and, as indicated by sole-oven expansion results, would require blending with lower rank coal to avoid oven damage.

Jan 1, 1963

The primary steel industry of the Prairie Provinces consists essentially of three companies whose total annual melting capacity, as of January 1, 1963, was 333,000 net tons. These companies have steel rolling facilities. In addition, there are five other companies producing steel castings by melting scrap in electric furnaces which, with the plants having rolling facilities, gives a total annual furnace melting capacity of 380,000 tons. Since 1954, the annual production of steel ingots and castings has ranged from a low of 66,588 tons, in 1954, to a high of 211,138 tons in 1961. The present facilities on the Prairies for making steel ingots from scrap, and rolling them to produce light merchant mill products, appear to be sufficient for many years ahead. Steel scrap, as electric furnace feed to make steel ingots for the present line of products, will probably continue to be available at reasonable prices either on the Prairies or from the north-central United States. It is recognized, however, that residual elements in scrap may be-come of greater significance and necessitate more rigid control of scrap quality.

Jan 1, 1963

By R. W. Stahl

An award is a form of recognition given for superior performance in a special field of endeavor. Each year awards are given by the Joseph A. Holmes Safety Association and the National Safety Council to mineral industries' mines, quarries, and plants that have worked a specific number of man-hours without a lost-time injury. These awards have a dual significance in that they prove that efficiency can be attained without injury to persons. Safety awards do not result from luck or good fortune but do result from sincere desire coupled with sufficient effort and cooperation to achieve a desired goal.

Jan 1, 1963

By G. T. Krempasky

In an attempt to develop a suitable precast concrete support for underground use, two different models (1955 and 1958) of a five-piece concrete set were designed, fabricated, and tested under adverse loading conditions. Model 1955 was designed to withstand an ultimate, uniformly distributed, vertical load equivalent to what a three-piece, 12- by 12-inch wood set of intermediate-grade Douglas fir would withstand. A design figure of 138,000 pounds for the vertical load was used on both the 1955 and 1958 models. In addition, the 1958 model was designed to withstand a uniform horizontal load of 7,000 pounds per foot and additional concentrated-point loading. The step- by-step design of each model is presented in the appendixes. A series of five destruction tests was conducted underground on the 1955 model, and results of the tests showed that the type and method of blocking were of major significance.

Jan 1, 1963

By Sara Jane Boles

The purpose of this Bureau of Mines investigation was primarily to isolate and examine the effect of liquid content upon the apparent porosity and bulk density of compacts pressed from high-purity, fused aluminum oxide, and, secondarily, to study the actual mechanism by which the liquid content affects the bulk density. No attempt was made to approach the theoretical maximum density of the oxide by introducing additives, particle packings, or similar variables; instead this study is an intercomparison of the bulk densities obtained as functions of the water contents of the compacting mixtures. Water content was varied from 7 percent to 25 percent, on a total-weight basis. The data gathered indicated a well-defined optimum water content for obtaining minimum apparent porosity and maximum bulk density, under the conditions of the experiment. During the course of this study, a number of additional variables in the forming process were discovered and are introduced in this report, although a thorough evaluation was found to be beyond the scope of this present investigation.

Jan 1, 1963

By F. Weinberg

WHEN impure Zn (< 99.99 pct)&apos;&apos;Z or Zn-Cd alloys3 are progressively solidified, a cell or "corrugation" substructure4 is produced in the solid, with a high impurity or solute concentration along the cell walls. When these materials are polished and suitably etched, etch pits are often observed along the cell walls. For the Zn-Cd alloys these etch pits have been associated with decorated dislocations, present in the corrugation boundaries to accommodate the lattice strain. In the course of an investigation of Zn-2 pct Au alloy, molten metal of this alloy was poured into cold water and the resultant solid pieces were sectioned, polished and etched with a Cr0 ethant. An extremely regular cell pattern was observed on the etched surface, similar in general to the corrugation structure previously reported for impure zinc and Zn-Cd alloys. At higher magnification, regularly spaced pits were observed along the cell boundaries. An example of the regular cell pattern at the center of a specimen is shown in the center and lower portions of Fig. 1; the top of the figure shows the pattern near the specimen surface. Typical etch pits in the cell walls are shown in Fig. 2. It was surprising that a cell pattern as regular as that shown in the center of Fig. 1 was produced at the very rapid solidification rates used (estimated as > 1 cm per sec). In addition, the distribution coefficient for the Zn-Au system is greater than 1. Accordingly, the center of the cells should be rich in solute and should etch

Jan 1, 1963

By N Robb

This paper gives an account of the laboratory testing, plant testing and final inclusion of the two-stage sulphuric acid leaching process in the Milliken mill. Operational results for September, 1962, are presented, showing a uranium extraction of 95.5 per cent, with a saving of some 16 lbs. of 100 per cent H~S04 and some 9 lbs. of lime per ton milled. Methods for effecting further improvements in the process are indicated. HISTORY P RIOR to the incorporation of two-stage leaching, the process for the treatment of uranium ores at Milliken consisted of a single-stage sulphuric acid leach, followed by a solution recovery step involving washing in thickeners and two-stage filtration. The thickener overflow solution was subsequently concentrated and purified by ion exchange, and the uranium was recovered, by two-stage precipitation, as ammonium diuranate. Figure I illustrates this flowsheet. For satisfactory extraction of uranium from the. Milliken ore, a high residual acidity, of the order of 40 grams per litre of free acid in the discharge solution, must be

Jan 1, 1963

By J. E. Moyle

The costs of labour and electric power are of prime concern to almost all industrial enterprises, and various methods of reducing their impact on production costs are constantly being developed. Automation is one of these schemes, and has received a good deal of attention in the past few years. In the mining industry, compressed air is almost universally used, and its cost is significant. Although the compressor machinery now in use has achieved a high degree of development, the hazard of explosion and fire still exists in these systems. There is thus considerable resistance in some quarters to suggestions that such installations can be safely and successfully automated. The Milliken power plant consists of two 30,000 lb. /hr. fully equipped high-pressure boilers, four H.P. air compressors, a steam turbine for stand-by power, and several L.P. compressors and vacuum pumps. With the installation of automatic and protective equipment in the machinery section, the shift force has been reduced from three to two men.

Jan 1, 1963