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By J. D. Sunderkötter, M. F. Stroosnijder, V. A. C. Haanappel

"TiAI-based intermetallic compounds have attracted considerable interest as structural materials for high-temperature applications due to their low density and substantial mechanical strength at high temperatures. However, one major drawback hindering industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 °C. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium, and of the effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of such materials.Extended AbstractIntroductionTiAI-based intermetallics are being considered as construction materials for high temperature components, e.g. in aircraft and car engines, due to their low density and substantial mechanical strength at high temperatures, see e.g. [1,2]. The best ductility can be attained with alloys consisting of y-TiAI with around 5-15 vol.% Q2-Ti3AI. However, one major hindrance to industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 aG. In spite of their high aluminium content, TiAI-based intermetallics do not generally form long-lasting protective alumina scales. After longer exposure times the scales, which are initially rich in alumina, deteriorate and scales consisting of mixed alumina and titania predominate, with high growth rates similar to pure titania.It is not the intention of the present paper to present a general overview of the high temperature oxidation behaviour of TiAI based intermetallics, for which the reader is referred to the literature [3,4]. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium. The effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of these intermetallics will also be considered."

Jan 1, 1996

By S. A. Diatchkov

Introduction There is a misconception that mineral-project economic evaluations in the former Soviet Union are either nonexistent or very limited. This is not the case. In fact, there are at least two basic methods that can be utilized to evaluate the vast mineral resources of the Commonwealth of Independent States (CIS). Evaluation procedures are based either on a comparison to known projects, which may rely on limited available data, or on potential-profit calculations, which generally uses more extensive databases. Significant philosophical differences between these systems and those utilized in the Western world include the following: •Under the centralized-government system, the economic evaluation of a mineral project was based on artificially determined mineral prices and costs. Every ten to 12 years, prices for concentrates and metals were established by the Council of Ministers and remained unchanged until the next reconsideration of prices . •The time value of invested money was not considered to be important under these "stable" prices, and inflation was assumed to be nonexistent in the planned economy. •An overestimation of the value of social and economic factors such as keeping the local population employed and providing the country with strategic minerals biased the economic evaluations of projects. Sequence of exploration Geological exploration in the CIS countries typically includes two major phases: prospecting and exploration. Prospecting consists of the following: •Regional geological studies. •General prospecting. •Prospecting. •Prospect evaluation. Regional geological studies are conducted within large territories and utilize satellite images, deep seismic zoning and other state-of-the-art methods. Geological and geophysical maps on a scale of from 1:200000 to 1:1000000 are developed to help identify regional anomalies and mineral prospective areas. The areas of primary interest are then subjected to general prospecting, beginning with geological mapping of the area at 1:50000 (1:25000) scale. The prospecting phase determines mineral potential based on further geological mapping (mostly 1:10000 scale), surface geophysics and geochemistry. Finally, the most attractive targets are subjected to further detailed evaluation (prospect evaluation) to help identify "possible" projects by means of trenching and wide-spaced drilling. The results of the prospect evaluation are analyzed and conclusions regarding the economical potential of the project are drawn. If the initial-prospecting phase results are positive and the prospect is recognized as economical, it then moves into preliminary exploration, which is followed by detailed exploration. Preliminary exploration determines the feasibility of the project on the basis of limited data. For example, in some underground projects, the initial exploration drilling and tunneling is done at two or three times wider spacing than would be required by the assumed mining method. Detailed exploration focuses on preparing the project for mining development, such as completing drilling and tunneling, particularly in the portion of the ore body to be first mined. During the project's mining phase, further exploration is usually conducted along the flanks of the mineralized structures and deeper sections of the ore body. Finally, during exploitation, it is sometimes necessary to delineate the ore body within the mining-block limits. A comparison between the United States (US) sequence of exploration activities and the CIS system is given in the Table 1. There is no "additional" and "exploitation" exploration shown in the US system, but it is common knowledge that all mineral projects are subjected to "additional" and "exploitation" exploration while being mined. An economic evaluation should be performed after the [ ]

Jan 1, 1996

By J. E. Burke, C. S. Barrett

THE fine lines shown in Fig 1 are typical of markings that may be detected after polishing and etching deformed specimens of alpha brass and other alloys. Although they have long been the subject of discussion by metallurgists their nature is still uncertain and the names that have been applied to them, such as deformation lines or strain markings, indicate this uncertainty. In this paper which reports the results of a further investigation of their nature, they will be called strain markings. INTRODUCTION Matthewson and Phillips1 in 1916 concluded that strain markings appeared only after deformations that exceeded 20 pct. They objected to the markings being called slip lines believing this term should be reserved for surface markings produced by plastic deformation. In 1921, Vogel2 described similar striations which appeared after polishing and etching the roughly ground surface of numerous alloys. He reported that the markings were crystallographic in nature, and since they resemble Neumann bands in iron, at least superficially, he assumed them to be mechanical twins. In 1928, Matthewson3 reported work by Phillips which indicated that the lines were more readily produced by impact than by slow deformation and that in many cases the twins inside recrystallized grains were parallel to strain markings in the original deformed grains. This was taken as evidence that the markings coalesce into annealing twins, and hence that they themselves are mechanical twins. Many attempts have been made to [ ] demonstrate directly that the markings are mechanical twins. In 1934, Samans4 described the results of X ray studies of two deformed crystals of alpha brass. Evidence was obtained which could be interpreted to indicate that the strain markings are mechanical twins, and this remains the only direct evidence to this effect. Several other attempts to obtain similar evidence by X ray diffraction have failed5,6,7 although in no case was the original method of Samans employed. An

Jan 1, 1948

By J. H. Bulloch

A study of fatigue-crack growth in a rail steel and an associated weld metal showed that fatigue cracks in the deformed rail steel had slightly higher growth rates than in undeformed rail steel. The crack growth in the weld metal was appreciably faster than either and exhibited plateaux that were above the upper bound reported for rail steels, The cyclic-life curves showed that, over an indicated service period of 8 years, both the deformed and the undeformed rail steels should not be prone to fatigue failures under the defined mechanical conditions, For the weld metal, the cyclic-life curves indicated the possibility of premature fatigue failures but, as al the input parameters represented a 'worst case' situation, this assessment could wel be ultra-conservative. In the rail steels at low levels, the extension of the fatigue cracks occurred by ductile striated growth. At a Kmax level of 35 MPa .J/n, cleavage facets formed initially on the surface of the fatigue fractures, and their incidence increased with Kmax until the onset of fast failure, The microstructure of the deformed rail steel exhibited cleavage facets at a slightly lower Kmaxvalue, and contained more cleavage facets at a given K level, than the microstructure of the undeformed rail steel. The average size of the cleavage facets agreed well with the pearlite nodule dimensions of 60 to 100 ILm. The microstructure of the weld metal was much coarser and contained columnar grains. At al f.K levels, the dominant fracture mode was cleavage, with small isolated regions of ductile striated fatigue cracks. The size of the cleavage facets varied from 150 to 600 ILm, and such a variation may be explained by the fact that cracking generally occurs in association with the pro-eutectoid ferite phase, and that this phase is distributed along some boundaries of prior austenite grains and the boundaries of the coarser columnar grains.

Jan 1, 1987

By D H. Laubscher

The in situ rock mass rating system û IRMR - leading to the mining rock mass rating system - MRMR - for jointed rock masses has been used (and abused) in mining operations around the world for the past 27 years. Despite the recent development of elaborate design procedures and computer-aided design packages, MRMR remains one of the most versatile and practical mine design systems available. It is important to realise that the rock mass classification system should not be replaced but rather complemented by more sophisticated and detailed design procedures. The classification system is not only the æcrudeÆ method used for initial assessment (as described in some geotechnical literature) but also in many respects a very effective and practical engineering tool. MRMR could, and should be used during the entire stage of mine life as an integral part of the design process. The objectives of this paper are to illustrate using practical case histories from the past decade, some of the pitfalls of the MRMR classification system, to clarify certain misconceptions in its application and update its mining application.

Jan 1, 2000

By Erwin Zodrow

An elaborate model for the magnetite distribution and genesis in the Smallwood mine, Labrador, based on factor analysis with orthogonal and oblique rotation of the factors, was proposed in an earlier paper. However, it is implicit in that model that variances of one variable shared with all others (communality) are estimated. To avoid the problem of communality estimation in the present investigation, a different type of factor analysis is used which (1) emphasizes the shared variances, and (2) attempts to eliminate, as much as possible, errors associated with the estimation of communality and sampling (unique variance). The samples for the present analysis are not the commonly employed oxide percentage variables, but counts of mineral species in specified areas of thin sections from drill core in the Smallwood mine: quartz, magnetite, calcite, and specular-hematite minerals. The counting procedure for mineral species is similar to modal analysis differing from it principally in the aspect of texture recognition. The constant area in which mineral species are counted is dependent primarily on

Jan 1, 1975

With the continued drop in export coal prices (as measured in US$) delivered to the Pacific Rim market, and a fixed annual 12 per cent increase in overburden, Usibelli Coal Mine Inc was faced with the need to reduce mining costs substantially or else forfeit its foreign coal contractual commitment which amounted to about half of annual mine output. Management made a difficult and fortuitous decision to proceed with an engineered plan to switch from a two seam, extended bench dragline operation to a two seam, cast blast and spoil side operation. While down-sizing and cut-backs became the rule in all departments of the mine, the drilling and blasting budget was more than doubled. Most will agree that this is contrary to what usually happens when a mine is faced with down sizing. The more common scenario would have management target the drilling and blasting budget for decrease as a first priority to cutting cost, and then later witness a decrease in equipment performance leading to an increase in the production cost per tonne. Although Usibelli Coal Mine more than doubled its annual drilling an blasting budget three years ago, the overall stripping cost has be, reduced by more then 37 per cent.

Jan 1, 1995

By F. W. Lee

Operating engineers and mining executives are interested in the science of applied geophysics, but are looking for a simple and understandable exposition of its problems, instead of dissertations which are becoming more and more involved and increasingly difficult to comprehend. It may be well to discuss the goal, the attempted methods of reaching it and the psychological motive, if any, tack of the science. Where does the subject of applied geophysics stand from the viewpoint of (1) the physicist, (2) the mathematician, and (3) the geologist? Fundamentally, the science aims at a differentiation of subterranean geology with the object of finding useful mineral products by the study of gravitational, magnetic, seismic, electric, and other fields which may be associated with the materials naturally or which may be applied to them. The more skillfully these fields are recognized, applied, and analyzed the greater will be the possibility of interpreting results in a way that will be remunerative both economically and scientifically.

Oct 1, 1931

The Burragorang Valley lies approx. 95 km by road south west of Sydney and some 35 km west of Camden. It is over 80 km in length and varies in width from 3 km to over 16 km. Geologically, the history of the Burragorang Valley is of interest. It was referred to by early geographers and N.R.M.A. booklets as the largest sunken valley in Australia. This description is incorrect as it is a water worn valley formed by the dissection of an uplift in the south western portion of the large Sydney Sedimentary Basin. Ages2 ago there extended right across the Blue Mountains, a continuous tableland into which the Nattai, Wollondilly and Cox's Rivers have carved out the formation of the Burragorang. This dissection together with other valleys such as the Megalong, Jamieson and Grose, formed part of the eastward drainage pattern of the uplifting tableland into the Pacific ocean. The lapse of time since the streams in the Burragorang began their work of erosion can

Jan 1, 1976

This paper sets out to discuss how alluvials - particularly mineral sands, tin and gold have adjusted to meet the problems of lower grade and more difficult physical political and economic conditions. The mineral sands industry seems to have adapted satisfactorily but less so with tin and gold.

Jan 1, 1996

By R. Daignault et G. O. Allard

The Chibougamau area represents a part of the Abitibi greenstone belt. The rocks constitute a volcanic pile (Roy Group) overlain by a volcano-detritic sequence (Opemisca Group). Three important periods of tectonic deformation have been distinguished. The first one produced folds with north-south horizontal axes. The second one is responsible for the isoclinal east-west folds, and the associated regional schistosity. Reverse faulting contemporaneous with this period of deformation, produced two distincts effects. In some cases the faults cause a repetition of the stratigraphic sequence. Whereas in others the faults truncate second period folds. Domes and basins interference pattern are produced by the superposed effect of Di and D2 deformations. The motion of these two periods would be more or less contemporaneous. The deformation could be generated by rising diapirs of early plutons combined with the progressive formation of troughs by gravitational subsidence of denser strata. The rising diapirs of late granitoid plutons produces a wraparound of the host strata.

Jan 1, 1984

By Osamu Iida

In the Mitsubishi converting furnace (C-furnace), molten matte continuously undergoes intensive conversion into blister, and an excess amount of heat is generated, even after taking into account heat loss from the furnace, off-gas, and latent heat of melt. To absorb excess heat in C-furnace, recycled granulated converting slags (C-slag) were wastefully charged in the C-furnace. In contrast, supplementary coal is necessary to make up a shortage of reaction heat in Smelting furnace (S-furnace). To utilize the excess heat of the C-furnace effectively and accommodate the unbalance of heat utilization between S and C furnaces, three technological innovations had been carried out. ? Spent anode charging facilities in C-furnace was modified, in order to solve some spent anodes hitting and eroding the hearth bricks. ? Cubic pressed copper scrap charging facilities were installed in C-furnace. ? Facilities were newly installed in C-furnace to treat neutralized residue from the wastewater and dust treatment plants, previously treated in the smelting furnace. Above innovations led to the further effective utilization of heat, increase in production, and savings in energy costs.

Jan 1, 1999

By Chase Palmer

INTRODUCTION. WHILE the reducing action of organic matter, of ferrous sulphate, and of hydrogen sulphide has frequently been invoked to account for the deposition of native gold and silver from ore-forming solutions, the high efficiency in this respect of certain of the metallic minerals which form the ore itself has not been sufficiently recognized. If a little finely powdered chalcocite is placed. in a test-tube and 2 or 3 cc. of a dilute solution of gold chloride are poured over it, two or three shakes of the tube suffice to remove all the gold from the solution. The color of the solution changes from yellow to pale green, showing that copper is dissolved simultaneously with the precipitation of metallic gold. If a piece of chalcocite is hung in a dilute aqueous solution of silver sulphate (1 normal), a coating of silver begins immediately to form on the mineral, and within a few moments a beautiful silver tree has developed, similar to that formed when metallic zinc is immersed in a similar solution.

Jan 5, 1913

By Edwin Higgins

INTRODUCTION IT is the purpose of this paper to set forth the relation and functions of the various organizations and institutions engaged in the promotion of safety iii the iron mines of the Lake Superior region; also to indicate the value of this work. Ten to 15 years ago there was practically no organized safety work; the accident rate was high, excessively so in some districts, and dangerous practices and conditions existed in many of the mines. During recent years, however, a gradual change for the better has been made. The chief causes of this change have been (a) public opinion, which has set the stamp of disapproval on the disregard for human life; (b) certain State laws which have made the operators responsible in dollars and cents for injuries to workmen; and (c) the humanitarian attitude of many of the operators, who have always decried the great loss of life in the mines. Today the Lake Superior region as a whole stands second to no other metal-mining district in the United States in its efforts to promote the welfare and safety of the miner. Dangerous practices in and about the mines are fast disappearing. The operators are ready and eager to adopt any expedient, rule, or device that holds forth a reasonable promise of reducing the hazards of the miner. Today the value of a mine captain or shift boss is reckoned, not alone on his ability to "get the ore," but also on his capacity for reducing accidents. While the progress made has been remarkable, there still remains much to be done, for the accident records of the Lake Superior iron mines, while lower than those of the chief metal-mining regions of the United States, still compare unfavorably with those of the metal mines of practically all foreign countries.

Jan 10, 1914

By Å Sandström

Loussavaara-KiirunavaaraAB?s (LKAB) iron ore mine, Kiirunavaara, is of magnetite type and associated with apatite, a calcium phosphate mineral. Rare earth elements (REE) have been found in connection with the apatite but also in other minerals. An apatite concentrate was produced by flotation, in order to investigate the possibilities to extract REE from the apatite by hydrometallurgical means. The content of rare earth elements calculated as oxides (REO) was 0.44% in the concentrate. Initially, leaching was done with large excess of sulfuric acid, hydrochloric acid, and nitric acid to study the REE solubility with different acids. In sulfuric acid, the leaching recoveries of the different REE varied between 35% and 69%. The reasons for the relative low recoveries, were that the rare earth elements precipitated together with huge amounts of gypsum, that was formed during leaching. However, both hydrochloric- and nitric acid gave almost complete extraction of the REE into solution. Analysis of the small leaching residue obtained, revealed, that mainly the light REE remained in the residue indicating that a small part of the light REE were present in the concentrate, in some acid, insoluble mineral other than apatite. With the aim to separate the REE from the phosphoric acid, the solutions from hydrochloric- and nitric acid leaching were neutralized to a pH of approximately 2 with ammonia. During neutralization, REE were precipitated as phosphates with good recoveries and a concentrate of 10.5% REO suitable for further upgrading was obtained, while the remaining solution can be used for fertilizer production. In further solvent extraction studies, it was shown, that after re-dissolution the REE could be effectively extracted by Cyanex 923, thus allowing for purification from calcium and phosphate ions. The REE were finally stripped from the organic phase and a REE nitrate solution was produced. Keywords: apatite, rare earth elements, REE, leaching, solvent extraction, cyanex 923

Sep 1, 2012

By L. W. Saperstein

In this paper, a number of novel hypotheses that provide a fresh perspective on the characterization of strata movements associated with longwall mining are developed by analyzing subsidence measurements with an influence-function-based computer program. Using an inverse application of the traditional influence-function technique, easily obtained surface displacements are used to analyze some of the complicated, expensive, and difficult-to- measure movements of the intermediate roof strata in a longwall panel. The primary hypothesis developed by this analysis proposes the existence of an area of partial roof caving near the edge of a panel called the "edge effect." A secondary hypothesis, interrelated with the first, promotes the importance of the effect of gate-entry closure on the observed strata movements. Both the primary edge-effect hypothesis and the secondary hypothesis concerning gate-entry closure are justified and quantified in an extensive analysis of surface subsidence that uses supporting information from related theories, design criteria, and in situ measurements. Next, the edge effect and the gate closure hypotheses are extended further and used to provide an explanation of the complex subsidence interaction of adjacent longwall panels in what is termed a "redisturbed" effect. Finally, the importance of accurately understanding these longwall strata movements for proper subsidence prediction or gate design is stressed.

Jan 1, 1988

By R. W. Bartlett

The extensive central Idaho black sand placer deposits are a potential source of rare earth elements, particularly the heavy rare earth elements that are not prevalent in commercial bastnasite deposits. These placers derive from the Idaho batholith. The geology, occurrence, and extent of these deposits are reviewed and the diverse mineral assemblages and complex mineral chemical compositions of these sands are described. Niobium, yttrium and thorium are also present in significant concentrations. The results of prior mining practice, including concentration and separation of the heavy minerals are reviewed. Technical approaches to extraction of rare earths from Idaho black sand concentrates are discussed.

Jan 1, 1992

By G. Gutierrez, D. A. Elgillani, M. C. Fuerstenau

The zero-points-of-charge of apatite, calcite, and fluorite are pH 6.4, 10.8, and 10.0, respectively. Scheelite is negatively charged above at least pH 3. In this article, the flotation responses of these minerals in the presence of potassium oleate and sodium silicate are described and compared with electrokinetic data. Colloidal silica appears to be the species principally responsible for calcite depression, while silicate anion is the species responsible for fluorite depression. Additions as high as 1 x 10-3 mole/liter silicate have no effect on the flotation responses of apatite and scheelite. Selective flotation of nonmetallic minerals is difficult to achieve with fatty acids or soaps by themselves. As a result, specific reagents are added to aid these separations, and one of the reagents commonly employed for this purpose is sodium silicate. Flotation separations of various calcium-bearing minerals such as fluorite from calcite1-3 and scheelite from calcite2,4 and apatite,2,5 for example, almost always involve the use of sodium silicate. The mechanisms by which sodium silicate functions as a depressant are still not understood, probably for a number of reasons. For one thing, the dissolution process of sodium silicate is complex, giving rise to a number of ionic and colloidal species.' Moreover, the type and concentration of these species depend on the ratio of Na2O to SiO2, the concentration of sodium silicate, and the pH of the system.' At the present time, it is not known which species, colloidal silica or silicate anion, is responsible for depression. If colloidal silica is the species that is adsorbing, then adsorption must occur by electrostatic attraction between the colloid and the mineral surface. Silicate anion, on the other hand, may adsorb either physically or chemically. The objective of this paper is to determine first the active species of sodium silicate and then the conditions under which this species will adsorb and function as a depressant. EXPERIMENTAL MATERIALS AND METHODS Pure samples of apatite (Durango), calcite (Iceland-spar), fluorite, and scheelite were used in this investigation. Pure potassium oleate was used as collector, while reagent-grade HC1 and KOH were employed for pH adjustment. The sodium silicates used were samples obtained from the Philadelphia Quartz Co. In one series of experiments, various sodium silicates containing different ratios of SiO2 to Na2O were added to calcite systems. These sodium silicates contained SiO2-to-Na2O ratios of 3.75 to 1, 3.22 to 1, 2.40 to 1, and 1.60 to 1. All other experiments were conducted with the sodium silicate containing the ratio of 3.22 to 1, which is the one that is normally used in industry. Flotation experiments were conducted with 21/2-g charges of 48 x 150-mesh material in conductivity water with an apparatus and technique described previously. Electrokinetic experiments were conducted with both a Zeta Meter and streaming potential apparatus. Particle size was 48 x 65 mesh for the streaming potential experiments. EXPERIMENTAL RESULTS The first series of experiments involved flotation of scheelite in the absence and presence of sodium silicate. As shown in Fig. 1, flotation response was not affected with even the relatively high addition of 1 x 10-3 mole per liter sodium silicate. Interestingly though, no flotation was effected below pH 6 with this collector addition. The responses of apatite to flotation under these same conditions are given in Fig. 2. Similarly, no depression was obtained in basic media under these conditions. Similar experiments were conducted with fluorite, and in this case, depression was noted above about pH 11 with 1 x 10-3 mole per liter sodium silicate (Fig. 3). When calcite was floated with these same levels of addition of sodium silicate, essentially no flotation was possible above pH 7 (Fig. 4). The effect of collector addition with a constant addition of sodium

Jan 1, 1969

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

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