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By O. Katz, A. Spilners, M. Simnad

THE oxidation of titanium has been studied in recent years by a number of investigators.'-W ne of the most important aspects of the reaction of titanium with oxygen, which has been observed by several of the investigators, is the extremely high solubility of oxygen in the metal. A detailed study of the Ti-0 systeml% as shown that the solubility limit of oxygen in a-titanium is approximately 14.5 wt pct 0 from 800" to 1700°C. The unusual oxidation behavior of titanium may be ascribed to this phenomenon, since part of the oxygen uptake enters into solid solution in the metal and only a part is available for scale formation. A more complete study of the kinetics of oxidation of titanium would require information on the influence of oxygen in solution in the metal upon the oxidation rate. Such information would also be of interest in regard to the theory of oxidation of metals. The authors have measured the oxidation rates of oxygen-saturated and oxygen-free titanium between 800" and 1200°C and have found appreciable differences in their rates of oxygen uptake and in the activation energies. The experimental set-up was similar to that described in a previous paper.u The course of oxida-dation was followed continously by attaching the specimen to a sensitive spring balance and observing the extension of the spring with time of oxidation. High purity electrolytic oxygen was used and precautions were taken to purify the gases employed. The specimens were prepared from iodide titanium and were ground on metallographic polishing papers to a fineness of 4/0. The furnace was first evacuated and filled with argon; the specimen was lowered into the furnace, which was then evacuated and filled with oxygen, after the specimen had reached the oxidation temperature in argon. The samples were presaturated with oxygen by means of the following procedure: Each specimen was first heated in oxygen at 1200°C until its increase in weight indicated 13.8 pct by weight uptake of oxygen. The furnace was then immediately evacuated and filled with purified argon five times. The specimen was heated in the argon atmosphere for a period of 72 hr at 1200°C in order to saturate the metal with oxygen by complete absorption of the scale. The temperature was lowered to the oxidation temperature, the furnace was evacuated and filled with oxygen, and the oxidation rate was followed by noting the extension of the spring balance. No oxide film was visible on these specimens at the start of the oxidation experiments. Titanium samples in the oxygen-free as-received condition were also oxidized and their oxidation rates measured. The results are shown in Figs. 1, 2, and 3, which indicate that the initial rates of uptake of oxygen by both the oxygen-saturated and oxygen-free specimens are parabolic at these temperatures. The rate of uptake of oxygen is, however, appreciably lower

Jan 1, 1956

By J. H. Wernick, S. Geller

A number of new AB, compounds, in which A is a rare earth or yttrium atom and B is Al, Mn, Fe, Co, or Ni, having the cubic MgCu, structure (Laves phase) are reported. In most of the compounds, the interatomic distances are normal; the lanthanide contraction is observed. However, in the compounds CeB2, B = Fe, Co, Ni, Ce appears to have a valence substantially greater than three; in CeAl2, Ce appears to be trivalent. These results are interpreted as vesulting from an energetically more favorable situation for the 4f electron of Ce to be lost to the 3d band of Fe, Co, nnd Ni. Evidence for the existence of homogeneitj! ranges in these compounds is presented. THE purpose of this paper is to report on the crys-tallographic investigations of a large number of new compounds, Table I, with the MgCuz structure (cubic Laves phase). It is a part of a continuing study of the magnetic properties and structures of binary systems involving the rare earths. In a previous paper' some of the magnetic properties of such systems were reported briefly. We have also reported2 a number of compounds of the CusCa type. The compounds were prepared by induction melting in Argon atmosphere of mixtures of stoichiomet-ric amounts of the constituent elements.* For most of the compounds fused alumina or silica crucibles were used as the containing vessel; graphite crucibles were used to prepare CeA12, NdAl2 and TbA12. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis-type Norelco cameras of 114.6 mm diam. The compounds AB2 belong to space group Fd3m-Ol with 8A in a): (000; 01/2 '/2;3) + 000-; b % XA and 16B in dl: (000; oVa %; 3) + 5/87; % %; 7e % Vs\£>. Because the intensities of the reflections on the powder photographs of the different compounds are similar, relative intensities were computed only for DyMnz for CrKa radiation, Table 11. In the calculation of intensities, the Thomas and umeda3 atomic scattering factors, corrected for dispersion,4 were used. The agreement between observed and calculated intensities leaves little doubt that DyMnz has the MgCuz structure. Crystallographic data for the ABz compounds are given in Table JII. Twelve of these compounds have been reported by other authors. A comparison of the published results with our work is given in Table W.* ers of elements of lower purity, to peritectic reactions in some cases, and to the presence of homogeneity ranges in these alloys, so that melting losses would still result in single phase alloys. The possibility of existence of homogeneity ranges in these compounds was investigated systematically only for GdMnz. At room temperature, the solid solution range is between

Jan 1, 1961

By G. A. Koehler

The Hiawatha mine, a producer of iron ore, is near the City of Iron River, in Iron County, Michigan. This mine, operated by The M. A. Hanna Co., has been chosen by the author as a typical iron mine in this district that is using the cut-and-fill mining system. General Geology The Hiawatha ore body lies along the steeply dipping north limb of a syncline that closes around on the east end to form a bathtub-shaped structure. Throughout this major structure there are very many smaller wrinkles or folds, which vary the direction as well as the thickness of the ore body. The total length of the ore formation with minor interruptions so far developed is about 3600 ft. The ore body throughout the entire present depth of 2000 ft. has averaged approximately 40 ft. in thickness; it is somewhat narrower at the upper levels and shows a marked increase in thickness on the bottom levels. This increase in thickness probably indicates that the bottom of the trough is near or that a major monoclinal fold has been encountered, which flattens the ore and gives apparent horizontal thickening. The footwall of this ore body is generally a black, graphitic slate, very rich in iron sulphides, quite combustible when exposed to air, and very treacherous to handle during mining operations. The hanging wall, in most places, is a cherty, fairly hard iron formation, and in general stands quite well ill open stopes. There are places, however, where black slate is found in both the hanging wall and the footwall, which makes mining difficult, as the black slate tends to slough off after being exposed to air. In these places it becomes necessary to leave a scale of ore 5 to 6 ft. thick on both hanging wall and footwall, which is not recovered. Fig. I shows a typical vertical cross section through the Hiawatha ore body. Type of Stoping Because of the size and shape of the ore body and the hard, dense structure of the ore, sublevel stoping has been an efficient and economical method of extracting the ore. This method, with various minor changes, has been used since the mine was opened in 1893. There have never been any stope-filling operations, however, until recent years, when crushing of pillars and black-slate fires forced the issue and methods were arrived at to fill all stopes. Development of Deeper Levels Shaft sinking to deeper levels in development operations has been done successfully by two methods without interference or hindrance to production. These systems are: I. Sinking an auxiliary winze a short distance from the shaft, then drifting back to the shaft location and putting up a pilot raise through to the bottom of the shaft. This raise is always in the manway compartment of the shaft, so that no work is ever done under a cage or skip. A 20-ft.

Jan 1, 1946

By Nelson B. Russell, Donald C. Bond

The effects of various antifreeze agents on the formation of hydrogen sulphide hydrate have been studied. On a molar basis the relative lowering of Tm (the maximum temperature at which solid hydrogen sulphide hydrate can exist in equilibrium with the given solution) for the various agents is: sodium chloride 1.00, calcium chloride 1.71, methyl alcohol 0.57, ethyl alcohol 0.68, ethylene glycol 0.73, diethylene glycol 0.73, sucrose 0.87, dextrose 0.71. On a weight basis the relative lowering of TM is: sodium chloride 1.00, calcium chloride 0.91, methyl alcohol 1.08, ethyl alcohol 0.89, ethylene glycol 0.69, diethylene glycol 0.41, dextrose 0.23, and sucrose 0.15. Introduction The solid hydrate of hydrogen sulphide, H2S.6H20,1 is in equilibrium with water and liquid hydrogen sulphide at 85°F at a partial pressure of hydrogen sulphide approximately equal to the vapor pressure Of hydrogen sulphide at that temperature. At temperatures below 85°F, in the presence Of excess hydrogen sulphide (greater than the amount required to react with the water present) the hydrate is in equilibrium with liquid hydrogen sulphide at approximately the vapor pressure Of hydrogen sulphide. In the presence of excess water, the solid hydrate is in equilibrium with liquid water, containing dissolved hydrogen sulphide, at a pressure lower than the vapor pressure of liquid hydrogen sulphide at the same temperat~re.2 The lower the temperature, the greater the difference between the decomposition pressure of the hydrate and the vapor pressure of liquid hydrogen sulphide at that temperature. Conditions conducive to the formation of solid hydrogen sulphide hydrate may exist in wells producing a gas containing a high percentage of hydrogen sulphide under high pressure, or in the lead lines from such wells. This paper gives the results of tests made with various antifreeze agents which might be useful in decomposing the hydrate or in preventing the formation of the hydrate of hydrogen sulphide Apparatus Fig , shows a diagram of the apparatus used. The sample under observation was contained in a glass tube 34 cm long, having a 6 mm id and a wall thickness of 2.5 mm. The lower end of this tube was closed- with a plug of butyl rubber. The upper end of the tube was connected to a diaphragm gauge, with a stainless steel diaphragm, a manometer, a vacuum pump, and a cylinder of hydrogen sulphide, The tube was held nearly horizontal, with the liquid resting along the lower side of the tube. It was found that when the tube was held in a vertical position, it broke with ex. plosive violence as soon as it became filled with solid hydrate. Presumably this was caused by the expansion which occurred on solidification of the hydrate. The difficulty disappeared when the tube was held in an inclined position during the tests.

Jan 1, 1949

By Roy J. Helfinstine, Gilbert H. Cady

One of the most urgent needs in the field of coal combustion is the ability to predict the performance of a coal from knowledge gained from small-scale tests. Numerous types of analyses and tests are conducted on coal, including the proximate and ultimate analyses, heating value, varieties of sulphur, ash analysis, ash fusion temperatures, free swelling index, petrographic analysis, and Gieseler. plasticity. The Illinois Geological Survey has made an intensive study of the value of these tests for judging the performance characteristics of the coal as actually utilized. To date, three reports1,2,3 have been issued, and another is being prepared. The present paper briefly summarizes some of the results found in the studies. Equipment The equipment used for the tests is described in some detail in the above mentioned publications. Briefly, it consisted of a domestic stoker, cast-iron boiler, and water-cooled heat exchanger, which were operated as a forced circulation hot-water system. The entire unit was mounted on scales. Instruments for recording the per- formance of the coal included a hot-water meter to indicate the quantity of water flowing through the boiler; a two-pen, mercury-actuated thermometer to record the temperatures of the water entering and leaving the boiler; a chemical-type meter to record the percentage of CO2 in the stack gases; a pressure gauge to record the static pressure in the stoker-air duct; and a multipoint potentiometer to record the temperatures in the stack and room, and the opacity of the stack gases. A 16 mm motion picture camera was available for taking pictures of either the fuel bed or the scale dial. Procedure The tests described in this report can be conveniently divided into three phases. For the first phase, a load of 5 or 6 tons of unwashed coal (usually screenings) was obtained from each of fourteen Illinois mines. These coals were all crushed and screened to a size of 35 in. (square hole) by 8 mesh. Combustion tests were made on a part of this raw, screened coal. Another portion was passed over a concentrating table to reduce the ash to what was considered to be commercially reasonable, and combustion tests were made on this upgraded coal. The ash content of the remaining coal was reduced to a still lower figure by passing it over the washing table with greater reject, or by standard float-sink procedure. This cleaned fraction was then tested in the stoker-boiler unit. Thus three coals with varying ash content were tested from each mine. For the second phase reported here, coals were obtained from four Arkansas mines and tested as received and after passing over the concentrating table with a normal reject. One Illinois coal was tested in the "washed" condition only. The third phase included tests on commercially prepared stoker coals

Jan 1, 1950

By A. N. Holden, J. H. Hollomon

Inhomogeneous yielding during the early stages of plastic flow has been observed in many metals and has long been a subject of controversy. Low carbon steel, when strained at room temperature, exhibits a distinct yield point at which the metal ceases to behave elastically and begins to flow plastically without further increase in stress,† often with an actual decrease in stress from that existing at the yield point. One manifestation of this behavior is the familiar Lüders lines. The extent of the yield point elongation (the plastic strain which results without raising the stress above that at the initial yield point) may be several percent. Several explanations of this type of yielding in steels have appeared in the literature:1-3}; 1. The segregation of carbides or other constituents at the grain boundaries of ferrite forms cell-like blocks which break down at a higher stress than that at which the ferrite alone will flow. 2. The precipitation of various constituents within the ferrite itself in some way blocks initial flow until a higher stress is reached, after which a great deal of flow occurs without further increase in stress. 3. The restraining influence of neighboring, less favorably oriented grains in a polycrystal results in a storing up of energy, which on yielding is sufficient to cause the continued propagation of slip bands on the multiplicity of slip systems available in adjacent iron crystals without increase in stress. 4. Local segregation of carbon atoms increases the stress required for the initial propagation of dislocations. The stress required for further deformation is lower.3 Such an explanation would require the presence of upper and lower yield points in single crystals. Low and Gensamer2 have shown that heterogeneous yielding can be eliminated by removal of carbon and nitrogen from polycrystalline steels by wet-hydrogen treatment. They also demonstrated that the re-introduction of minute amounts of carbon or nitrogen caused a return of the yield point. Observations of the initial flow of single crystals containing small amounts of carbon and nitrogen- should provide a clue to the explanation of inhomogeneous yielding. Previous tests of iron crystals4-6 can not be considered conclusive because it is uncertain whether the carbon and nitrogen were satisfactorily removed by the decarburization technique employed. The purpose of the experiments described herein was to determine whether single iron crystals containing either carbon or nitrogen would exhibit in-homogeneous yielding. Experimental Procedures THE PREPARATION OF SINGLE CRYSTALS All crvstals were formed in the following way. Aluminum killed sheet material 80 mils thick was machined into specimens of the outer contour shown in Fig 1. These mildly tapered specimens were decarburized at 730°C for 16 hr in hydrogen that had been bubbled rapidly through water maintained at 70°. The resultant grain size after decarburizing was approximately ASTM 5. Several stress-strain curves were made of the decarburized niate-

Jan 1, 1950

By Stanley J. LeFond, Neal Davis

Drilling an oil well or most other types of drilling or coring is no longer a simple and uncomplicated operation. Drilling today at depths which exceed 9144 m (30,000 ft) is hazardous and requires personnel with long and varied experience in drilling. It also requires extensive experience and knowledge in the use of materials which are added to the drilling fluid or "mud," more often than not materials utilizing an industrial mineral. The drilling fluid can vary from a simple mixture of water and "mud" to a very sophisticated, scientifically compounded drilling fluid. Industrial Minerals Used in Drilling Fluids Industrial minerals which are commonly used in oilwell drilling and completion are listed in Table 1. The most important minerals, determined by sales, are bentonite and barite. The other minerals listed are either used to achieve a specific purpose or are used regularly but in limited quantities. The main suppliers of drilling fluids internationally are Magcobar Div., Dresser Industries, Inc.; Baroid Div., National Lead Co.; IMC Drilling Mud Co., (a subsidiary of international Minerals and Chemicals Corp. and Halliburton Co.); and Milchem, a division of Baker Industries. Most of the industrial minerals are found in North America, with barite mines and processing plants located in Nevada, Arkansas, Missouri, and Arizona, and bentonite mines near Graybull, WY. Other mines, such as those in Nova Scotia, are capable of shipping to South America and to the European and Middle East countries. Most of the materials processed by any of the suppliers must conform to specifications set by the American Petroleum Institute (API) or the Oil Companies Material Organization (OCMA). These specifications provide for uniform physical and chemical properties of the materials to be sold on the open market. Function of Drilling Fluids In the early days of rotary drilling, the primary function of drilling fluids was to bring the cuttings from the bottom of the hole to the surface. Today it is recognized the drilling fluid has at least ten important functions: 1) To remove the cuttings from the bottom of the hole and carry them to the surface. 2) To cool and lubricate the drill string and drill bit. 3) To build an impermeable cake on the wall of the hole. 4) To control subsurface pressures. 5) To hold cuttings and weight material in suspension when circulation is interrupted. 6) To release sand and cuttings at the surface. 7) To support part of the weight of drill pipe and casing. 8) To reduce to a minimum any adverse effects upon the formation adjacent to the hole. 9) To insure maximum information about the formation penetrated. 10) To transmit hydraulic horsepower to the bit. In order to accomplish some or all of these functions while penetrating formations of various characteristics, several types of drilling fluids systems have been designed. Types of Drilling Muds There are two basic drilling fluid systems-water-base muds and oil-base muds. There is a wide variety of groups within these two main

Jan 1, 1983

The Lornex mine is located in the Highland Valley area of British Columbia, Canada, one of the most,promising districts of low-grade porphyry-type copper mineralization in the world; Lornex is operated by Rio Algom Mines, Limited, a member of the Rio Tinto Zinc Group of London. Exploration from 1965 to 1968 disclosed an ore body of 293 million tons with a grade of 0.43% copper and 0. 14% molybdenum; this led to the decision to construct a 38,000 tpd operation, and production commenced in the fall of 1972. The ore is open-pit mined with 15 cu yd (11 5 m3 shovels, which load 100- and 200 -ton trucks. These trucks dump directly into a 60 in. by 89 in. Allis -Chalmers gyratory from two sides of the 14 ft 6 in. (4.42 m) deep dump pocket and across splitters mounted on the pocket sides. The unlined pocket would hold 1,000 tons level full. The crushedore discharges into a 300-ton surge hopper equipped with an automatic sonic level indicator to prevent over -filling. A 96 in. by 23 ft (2.44 m by 7 m) apron feeder delivers the ore from the surge hopper to a 72 in. (1.83 m) transfer belt equipped with a tramp iron metal detector. The transfer belt discharges to a 60 in. (1. 52 m) conveyor which conveys the ore about 3,000 ft (914 m) to the 475,000 ton ore storage pile located near the concentrator. Four 48 in. (1.22 m) pan feeders transfer the ore to the mill feed conveyors, which in turn supply the two 32 ft by 15 ft (9. 75 m by 4. 57 m) semi-autogenous mills, which easily accept the 10 in. (254 mm) product of the crusher. Each semi- autogenous mill is followed by a secondary ball mill. The unusually large open side setting of the crusher accounts for its 6,300 tph maximum capacity. Concentrator capacity is now 48,000 tpd. Eccentric removal is eased by the design of the door to the crushed ore pocket, which has the cart rails mounted on its outer surface and is lowered to a horizontal position in the pocket by an electric winch. The top of the door rests on wear bar covered concrete piers in the pocket. Another feature is a chute through the floor at the crusher base that extends into the crushed ore pocket. Dust and spills of ore on that floor during crusher repairs are easily swept into the crushed ore pocket. This feature is also used at Bougainville and Palabora and has been added to others after operation has commenced. The design follows the concrete rectangular box concept with four main service and maintenance levels shown in the sectional drawings, although a third additional section has been added at the maintenance

Jan 1, 1978

By Peter R. Morris, Alan J. Heckler

THREE angles are required to specify the orientation of a crystallite with respect to a physical reference frame. The distribution of crystallite orientations in a polycrystal is thus a function of three angular variables. The most widely used experimental techniques for studying orientation in polycrystals lead directly to the pole figure representation, i.e., the distribution of the poles of certain crystallographic planes in terms of two angular variables. In recent years1-5 methods have been developed which permit determination of the (three-angle) crystallite orientation distribution from several (two-angle) pole figure distributions. In this work Roe's method has been applied to the study of orientation in hcp materials. The method is illustrated for commercial purity titanium sheet (Ti-70) which was cold rolled (65 pct reduction), annealed at 1450°F for 3 min, and air cooled. The grain shape was observed to be equiaxed after this treatment. EFFECTS OF PHYSICAL, CRYSTALLOGRAPHIC SYMMETRY In Roe's method the crystallite orientation distribution, w(?,?,F), is expanded in a series of generalized spherical harmonics 11(?,?,F) = E E E W^Zirmtye-tote-in* [l] 1=o ,,,=-I ,,=-I where { = cos 8. The set of Euler angles employed here is illustrated in Fig. 1. The axis for each rotation is denoted by a double arrowhead. The positive sense of each rotation is that of a right-handed screw advancing in the direction of the double arrowhead. The X, Y, and Z directions correspond to the rolling direction, cross direction, and normal direction, respectively. In the initial orientation (10.O), (12.O), and (00 . 1) planes are perpendicular to the X, Y, and Z directions, respectively. The IC/ rotation about the Z axis is carried out first by rotating X into X', Y into Y', and leaving 2 unchanged, i.e., Z' = Z. The 8 rotation about the Y' axis is carried out second by rotating X' into X", 2' into Z", and leaving Y' unchanged, i.e., Y" = Y'. The I$ rotation about the Z" axis is carried out last by rotating X" into X"', Y into Y"', and leaving 2" unchanged, i.e., 2"' = 2". Any specified orientation of the X'", Y'", and Z'" crystal-fixed axis system relative to the X. Y, and Z physical axes (rolling direction, transverse direction, and sheet normal direction, respectively) can be obtained by appropriate IC/, 8, and (F rotations. The Zl,, of Eq. [l] are the Jacobi polynomials, augmented by the square root of the weight function. The Zl,, are symmetric in m,n, i.e., Zl,,= Zlnm. For orthotropic physical symmetry and hexagonal crystallographic symmetry, the coefficients, W!,,, of the series are all real, W!mn = Wzfi, = Wlm~ = Wlfi~, 1 and m are even and n is restricted to 6k, where k = ...,-2,-1, 0, 1, 2, .-.. The determination of the Wlmn from pole figure data has been previously described.'~~ The Zl,, may be written in multiple angle form

Jan 1, 1970

By R. L. Slobod, B. H. Caudle, R. A. Erickson

In predicting the sweepout pattern efficiency to be expected in a .secondary recovery operation, the reservoir engineer is often confronted with a situation in which part of the producing formation lies between the last row of wells and the reservoir boundary. To date, there has been little or no reference in the literalure to sweepout pattern efficiencies in such areas. This paper presents the results, of a laboratory study in which the area contacted around the edge of a reservoir injected in a five-spot pattern was determined. The X-ray shadowgraph technique was used in this study. It was found that surprisingly large portions of the reservoir area lying outside the well network are conracted by the injected fluid before, abndonment conditions are reached. In fact, it can he said that at least 00 per cent of the circa lying outside the last row of wells and within a distance of one well spacing of these wells will ultimately be contacted by the injected fluid in the case of most water floods. Frorn the results given in this paper, it is possible to estitilate not only the extent to which encroachment into these areas will occur but also the injection volume necessary to produce the wells to abnndonment conditions. INTRODUCTION While considerable work has hern done in recent years1.?.'.''.' evaluating the fraction of the reservoir contacted as a function of the mobility ratio for several different well patterns, there has been practically no mention of what happens to the oil in that portion of the reservoir which lies between the last row of wells and the reservoir boundary. In fact, the assumption is generally made that little or no recovery can he expected From this area. This assumption is incorrect and in many cases will lead to seriouq errors in calculating reservoir performance. The fraction of the area outside the regular well pattern contacted in a five-spot injection system has been studied using the X-ray technique5 to follow the progress of actual floods in porous models of reservoir elemental areas. In this paper, the method for carrying out such a study and the results showing the fraction of the area in question swept as a function of mobility ratio and the produced fluids are presented. THE REPRESENTATION OF A RESERVOIR BY ITS ELEMENTAL AREAS She portion of the reservoir lying between the edge of a reservoir and a line connecting the outermost wells may be roughly designated as the part of the reservoir outside the regular well pattern. An example of such an area is shown as the shaded portion in Fig. 1. The case of a square reservoir utilizing a five-spot injection program and with one full well spacing between the outermost wells and the boundary (Fig. 1) was selected as the single example which would provide the most insight into

Jan 1, 1956

By S. F. Urban, G. Derge

AT the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for a large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions [f] operation. The most important general conclusion reached was that the time a heat is held under a reducing slag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. PROCEDURE The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. Companion slag and metal samples were taken just prior to slag-off and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional 13 heats. Slag sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from tie furnace in a well-slagged carbometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace heats. The Big Wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 1 ½ in. long, and ¼ in. maximum thickness, and was finally adopted as the most satisfactory design. The Long Wedge Mold (b) was a 2 by 2 by 5 ¼ -in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 2 ¾ in. long, and ¼ in. maximum thickness. The Small Wedge Mold (c) was 2 by 2 by 4-in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 1 ½ in. long, and ¼ in. maximum thickness.

Jan 1, 1947

By Phillip Crowson

INTRODUCTION This discusses some of the economic risks and uncertainties which face any company investing in new mineral ventures. These differ mainly in degree rather than kind from other large capital intensive projects, except that economic risks are compounded with technical risks. Mines face a wide variety of physical risks, and in addition the ore reserves may not prove as ample, nor as amenable to treatment as the feasibility studies indicate. On the economic front, mineral projects are subject to risks of fluctuating prices and sales volumes, no matter where they are located, or how they are financed. Typically, they are heavy users of capital compared with their owners' internally generated funds. Long term debt of various types is still the favoured form of finance. A project's currencies and cost often differ from each other and from those of the parent company. Facing up to the various risks associated with fluctuating and uncertain revenues, interest rates and exchange rates are amongst the hardest tasks for natural resource companies. ATTITUDES TO THE MINING INDUSTRY Some have questioned whether the game itself is now worth playing. They have argued that the mining industry's mediocre rewards in the past decade have been insufficient, compared with the risks involved. They can see no prospect of dramatic improvement in the next decade. Demand is highly cyclical and tends to grow less rapidly than economic activity, as a whole. Barriers to entry are low in most mineral markets, but impediments to exit can be substantial. Exit is especially problematic in those minerals where there are large state shareholdings and/or where less developed countries are major producers. The consequence is claimed to be an endemic tendency to excess capacity, and prices barely adequate to cover marginal cash costs. Many of the petroleum companies that moved into mining with such high expectations in the late 1970s have retreated, often bearing the scars of heavy losses. Individual shareholders, taken collectively, place low valuations on their investments in mining companies. The price/earnings ratios of the major mineral producing companies are low compared with their historical averages and with those of other industries. PRICE: EARNINGS RATIOS (October 1988) [UK Industrials 12.0 RTZ 8.4 Cons Gold 12.2 US Industrials 13 - 13.4 Alcan Alcoa Amax Asarco Cyprus Minerals Freeport Copper Inco Inspiration Magma Copper Newmont Mining Nord Resources Phelps Dodge Reynolds Metal Canada TSE 300 10.6 Cominco 8.7 Falconbridge 5.3 Noranda 7.0 Rio Algom 7.2 Teck Corporation 17.] NOTE: Mining companies' p/e based on prospective 1988 earnings, from Kleinwort Benson Securities' weekly Mining World, October 1988. Until 1987, it was argued that share prices correctly reflected the companies' poor earnings potential. Subsequently, the argument has been that earnings have been unnaturally boosted by cyclically high metal prices. The stock market valuations, therefore, correctly reflect future earnings, or at least expected earnings. This seems to be a case of Heads, I win; Tails, you lose. The underlying analysis of metal markets appears

Jan 1, 1990

By David Turnbull

IN most reactions involving solids the transformation kinetics may be represented by the combination of two processes-those of nucleation and of growth. For example, Mehl and his coworkers 1,2 in their studies on the transformation of austenite to pearlite in steels have been able to describe the kinetics in terms of the rates of nucleation and of growth. By micrographic examination of their specimens they determined the nucleation rate (rate of appearance of pearlite colonies) as a function of time, of percent transformation, and of temperature. They observed that after an incubation period in which no nuclei are observed, the number of nuclei appearing per unit time per unit of untransformed grain boundary area, increases at an increasng rate with time. When recrystallization rates have been interpreted in terms of rates of nucleation and growth and the rate of nucleation determined, an incubation period followed by an increasing rate of nucleation has also been reported. Among the studies in which this phenomenon has been observed are those of Kornfeld and coworkers3 on cold-drawn aluminum wire, of Anderson and Mehl4 on the recrystallization of aluminum sheet, and of Stanley and Mehl5 on the recrystallization of silicon ferrite sheet. The existence of an incubation period during which no nuclei are observed does not appear to have been reconciled with the generally accepted Volmer-Becker theory of nucleation in condensed systems. This theory ostensibly requires the rate of appearance of nuclei to be independent of time. VOLMER-BECKER THEORY In order to form a stable nucleus of a new phase B in a mother phase A, the molecules or atoms of the mother phase must surmount a free energy barrier whose height is determined by the volume free energy change accompanying the transformation and the energy of the surface separating the two phases. The free energy difference between nuclei of various sizes and the molecules or atoms of the mother phase is plotted schematically in Fig I as a function of the radius of the nucleus r. This free energy difference is plotted for two values of the change of free energy per atom, (fB - fA) accompanying the transformation when the volumes of the two phases are infinite. One of these values of (fa-fA) corresponds to a temperature above the temperature To at which the phases A and B are in equilibrium, and the other to a temperature below To. In order for a nucleus of phase B to be stable at a temperature T2 < To, its radius must be equal to or greater than the critical value r* for which the free energy of formation of the nucleus is a maximum, ?f*. Aggregates of phase B having radii equal to or less than r* will be called embryos. Mehl and Jetter,6 in discussing the kinetics of nucleation in solid systems, suppose that embryos of critical size are formed

Jan 1, 1948

By A. J. Teplitz, T. Bardeen

In the course of an investigation of lost circulation, a new tool has been developed which gives a qualitative measure of the relative velocity between the fluid column in the borehole and the tool. The position of a diaphragm in the side wall of the instrument depends on the flow through the device. This position is established by using the conductive borehole fluid in a potentiometric circuit. The instrument has high sensitivity and can detect changes in velocity as low as. 5 ft/min. Lost circulation mud additives do not interfere with the satisfactory performance of the tool. In a number of circulation losses of the pressure induced type, the instrument has shown that the losses were confined to extremely narrow zones (less than I ft), indicating that such ruptures occur in a more or less horizontal rather than vertical plane as has often been assumed. This pinpointing of the zone of loss is important in remedial procedures since it allows the treatment to be applied directly to the point of loss rather than to the entire open hole. The device can also be employed for indicating points of entry of water in producing wells. INTRODUCTION The need for an improved means of locating the positions of lost returns zones became evident during an investigation of lost circulation difficulties in the Gulf Coast area.1 With instrumentation available at the time, it had been learned that, contrary to common belief, the position of the thief zone responsible for a given loss seldom coincided with the point of bit penetration at the time the loss was encountered. In the majority of cases, the losses were found to be occurring at some distance removed from the bottom of the hole —sometimes as much as a few thousand feet. This information, along with other observations made during the investigation, led to improved techniques&apos; for dealing with lost circulation problems. Highlighted, however, among the results of this work and of similar studies subsequently conducted in drilling operations in other parts of the country, was the indication that a considerable portion of the difficulty and expense involved in treating prolonged circulation losses is due to the unsystematic application of remedial measures to one or more apertures of unknown position. Basis of Tests It is worth considering that if the troublesome formation could somehow be transported to the surface where it could be directly observed, there would likely be little difficulty in readily effecting a seal. Although this is a decided oversimplification of the situation, it does appear that the chief obstacles to similar ease of handling of a lost circulation zone in a well are lack of visibility and of ready accessibility. The latter handicap is overcome to a considerable extent by placement techniques already in use, and other procedures now in the process of development are expected to offer further improvement. But in the matter of visual observation, the technique to be presently described appears to afford a quite satisfactory substitute.

Jan 1, 1957

By J. Leja, A. Pomianowski

This paper deals with equimolar solutions of xanthate and alkyl trimethyl ammonium bromide adsorption on copper, nickel and sphalerite powders. After an exposition of the experimental methods used and the results obtained, a thorough discussion leads to the conclusion that some molecular association between xanthates and CnTAB&apos;s does take place in the bulk of the solution as well as at the air/liquid interface. A spectrophotometric study of xanthate solutions alone and their mixtures with equimolar amounts of alkyl trimethyl ammonium bromide (CnTAB) has established the additivity of ultraviolet spectra (190 to 400 mµ) for potassium ethyl xanthate (KEtX) and C12TAB. No obvious effect of C12TAB addition on the decomposition rate of KEtX was observed, the half life of which was established as 29±3 days at 22°C and pH ~ 6. In mixed solutions of longer xanthate homologues (e.g. hexyl and nonyl) and equimolar CnTAB, colloidal precipitates are gradually formed which contain primarily the corresponding xanthate molecules. The kinetics of collector abstraction by copper, nickel and sphalerite powders were studied in 10-5 to 10"3 M solutions of KEtX alone and in equimolar mixtures of KEtX and CI2TAB. Presence of C12TAB caused a two to three fold increase in the amounts of xanthate (equivalent to many monolayers) abstracted by copper and nickel powders (and in their rates of abstraction) but had no effect on the abstraction of xanthate by unactivated sphalerite (equivalent to less than a monolayer). The adsorption of C12TAB itself from the mixed solutions was very low, at most one monolayer only, and was not influenced by the nature of the solid powder used. A change in the rates of abstraction, observed with copper powder, was interpreted as a completion of a multilayer coating (completely enveloping the grains of powder) following which the rate of reaction between solution and substrate becomes controlled by diffusion through this coating. Work of Buckenham and Schulmanl on molecular associations between different collectors has shown unusual synergistic effects in flotation of individual minerals using mixtures of xanthates and alkyl trimethyl ammonium bromides. The objectives of the present work were: 1) to determine whether these molecular associations between the two types of collectors (indicated by strong surface tension lowering in Buckenham and Schulman&apos;s work) take place at the air/liquid interface only or in the bulk of solution as well 2) to establish whether different solids adsorb any species from the mixture of these amphipatic molecules preferentially or as molecular complexes 3) to establish whether there are any differences in the kinetics of adsorption. Metallic copper and sphalerite powder were chosen as adsorbents since they represent two extremes since copper readily adsorbs multilayers of xanthate (and is easily floated with ethyl xanthate) while unactivated sphalerite does not appreciably adsorb xanthate but is known to be readily floated by the amine type collectors. Metallic nickel was included because the infrared spectroscopic work2 on xanthate

Jan 1, 1964

By G. W. Jones, G. S. Scott

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer&apos;s intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist&apos;s knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

NEW YORK SECTION ALLEN H. ROGERS, Chairman, H. C. PARMELEE, vice-chairman, FOREST RUTHERFORD, Vice-chairman, W. S. DICKSON, Secretary, 71 BROADWAY, NEW YORK, N. Y. J. E. JOHNSON, JR. F. T. RUBIDGE, Treasurer, P. G. SPILSBURY A meeting of the New York Section was held at The Machinery Club on Friday evening, Oct. 4, 1918, The Chairman, Allen H. Rogers, presiding. The CHAIRMAN.-MOST of us, I suppose, have been affected more or less by The request of The Fuel Administration that we leave our automobiles standing in The garages on Sundays. We shall all be interested in hearing about The situation that has called forth This, request, and The Oil Administrator, Mr. Requa, has kindly come from Washington to Tell us about it. MARK L. REQUA.-I am very glad To Tell you about the oil problem during This war period. The United States is supplying by far The greater part of all The petroleum products consumed in Great Britain, France and Italy. In addition To This, we have had To supply a marked increase in our domestic consumption, not only of The refined products, but of fuel oil as well. The combination has put a strain on The oil industry, which it is very difficult To meet. The oil companies, being under contract, had no option as To who should get Their oil first, and They were delivering pro rata To everybody; manufacturers of furniture were getting oil with The same regularity as Those who were making aeroplanes or munitions, and The oil companies felt that something should be done. The first order with which I had. anything To do was The priority list for The delivery of fuel oil. That list contained 12 classifications, beginning with bunker fuel and railroads, and you will realize The complexity of The situation when you hear that munitions plants are in class 11. The priority list held during The winter, but transportation became so bad, because of The number of ships that were Taken for trans-Atlantic use, that some of The oil companies were not able To deliver more Than about 60 per cent. into class 5, and nothing beyond that point. To add To the Troubles, the Tank-car mileage fell off. The average for 1917 was about 36 miles per car per day. in January, 1918, it dropped To about 8 miles, and it must have been nearly zero in The early part. of February. Because of The extremely severe winter, furthermore, pipe lines were not delivering anywhere near Their normal capacity. A new priority list has recently been promulgated, introducing a few slight changes. Natural gas has been brought under its provisions, and it has been extended To include The Pacific Coast, which was not considered necessary last winter. The situation in The gas industry is not satisfactory; it is estimated that There will be a decrease of 10 To 20 per cent. in The quantity of natural gas available This winter, as compared with last winter.

Jan 11, 1918

By Rollin E. Hook, Attwell M. Adair

The response of CrzO3 and C~304 to various heat treatments was studied in are-melted iodide chromizim over the temperature range 1000" to 1750°C. These oxides, which are present as impurity phases in this material, were identified by X-ray diffraction teclzniques which were supplemented by optical metallop-aphy. As a function of increasing temperature, Crs04 is first observable in samples annealed at 1300°C and coexists with Cr2O3 (the low-temperature oxide) over a temperature range exceeding 200°C. As the temperature decreases, Cr3O4 dissolves with the concomitant precipttation of Cr2Y2. Both oxides precipitate predominantly at pain boundaries. The reactions which occur are involved with at least ternary equilibria, possibly due to iron which is present as an impurity in arc-melted iodide chromium. HILTY, Forgeng, and Folkman&apos; reported in their investigation of the Fe-Cr-0 system that Cr3O4 (with about 8 pct Fe substituted for chromium) is a primary phase found in alloys with 9 or more pct Cr. They reported that this phase is stable only at high temperatures and that below the liquidus Cr3O4 is disproportionated into Cr2O3 and chromium-rich metal for both Fe-Cr-O alloys and in oxygen saturated pure chromium. Further, they proposed that CrsO4 forms by a peritectic reaction between Cr2O3 and the liquid. On the other hand, Hook, Garrett, and Adair2 found in their investigation of impurity phases formed in "pure" chromium (material consolidated from iodide chromium crystals) that Cr3O4 forms intergranularly and is stable as low as 1500°C which is 375OC below the melting point of chromium. The purpose of the research described herein is to determine the temperature range of stability of Cr3O4, and to show the nature of its decomposition. This further investigation indicates that Cr3O4 undoubtedly occurs in this material as low as 1300°C. The chromium studied was consolidated and fabricated from iodide chromium crystals (ICr-5) and contained Fe r 135 ppm, Si = 20 to 100 ppm, and 0 = 35 to 137 ppm. A complete chemical analysis is given elsewhere.&apos; Annealing was conducted in 1 atm of purified helium and all samples were rapidly cooled (-200°C per sec) by withdrawing them from the furnace hot zone under a high flow rate of helium. The details of the electrolytic-etching technique and electrolytic-digestion techniques for preparation of insoluble residues for X-ray examination are given elsewhere also.&apos; EXPERIMENTAL RESULTS The Starting Material. The as-swaged rod (final swaging done at 900°C) had a wrought grain structure and contained a dispersion of CrzO3 inclusions of maximum particle size of about 2 or 3 p, Fig. 1. The microstructure also contained a dispersed

Jan 1, 1964

By H. W. Schadler

Single crystals of tungsten, which were grown by electron bombardment floating zone refining, were strained 2 pet in tension and bending at 298°, 77°, and 20°K to determine the modes and crystallography of the plastic deformation of these temperatures. At 77° and 20°K plastic deformation occurs by slip on systems of the type (011) [111] and by twinning on (112)-type planes. For crystals strained at 298°K, deformation occurs by slip in [111] directions on either (Oil)- or (112)-type planes. CURRENT models for the initiation of brittle fracture in crystalline materials are based on a knowledge of the details of their plastic deformation.1 Body-centered cubic tungsten exhibits brittle failure at temperatures below about 500 °K yet the modes and crystallography of its plastic deformation have not been studied below 1000°K. In 1924, Goucher2 reported that tungsten single crystals with a total impurity content of less than 0.01 wt pet deformed by slip on the (112) [111] system in the temperature range 1000° to 3000°K. He also observed (001) [010] slip in one crystal which was constrained by the presence of a large fissure. According to Barrett3 tungsten also deforms by twinning on the (112) plane in the [111] direction, but he gives no details on the tendency for twin formation or the temperature range in which twinning occurs. Therefore, as a necessary part of a study of the factors influencing the brittle fracture of tungsten, the modes and crystallography of the plastic deformation were determined at 298°, 77°, and 20°K. Tungsten single crystals, grown using the electron-bombardment zone-refining technique first described by Calverly,4 were deformed to between 1 and 2 pet plastic strain in tension and bending. The surface offset resulting from slip or twinning was observed with an optical microscope to determine the crystallography of the deformation. The existence of twins was proven by the standard polishing and etching technique; and the crystallography of dislocation motion was followed using the dislocation etchant described by Wolff.5 Some observations on the fracture characteristics of tungsten single crystals are included. EXPERIMENTAL TECHNIQUES Growth, Purity, and Perfection of the Crystals-Several years ago Calverly, Davis, and Lever4 dem-onstrated the feasibility of growing tungsten single crystals by the electron-bombardment floating zone-refining technique, and Carlson6 showed that crystals produced in this way had a high degree of purity and were ductile at room temperature. Tungsten single crystals produced by this technique in equipment similar to that described by Carlson were used in this study. The starting material, a powder metallurgy product, was obtained in the form of a swaged 1/8-in. rod from the General Electric Wire Plant in Cleveland, Ohio. The crystals were grown from this material in a vacuum of 10"4 mm of Hg by passing a molten zone 1/8 in. long down the rod twice at a speed of 3 mm per min. At this zone speed

Jan 1, 1961

By G. S. Scott, G. W. Jones

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer&apos;s intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist&apos;s knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942