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By W. C. Ellis, E. S. Greiner

Metallic titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arke12 and Fast prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kr0ll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725 C," it may be classed as a light metal since the specific gravity is 4.5 g per cc-I. The crystal structure is close-packed hexagonal from room temperature to 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat,8 electric resistanceg and theimoelec-tric force10 at temperatures near 890°C. It is reportedll that annealed titanium has a tensile strength of 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between — zoo and I000 C have been determined. Materials For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was made from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at I000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was made from a rod of titanium, 0.19 in. in diam, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table 1. Oxygen and nitrogen which Were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1949

By Terkel Rosenqvist

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp p/RT, where p is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By Laurence Delisle, Aaron Finger

THE alloys formed by the addition of nickel to iron by convelltional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.? owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect could be obtained in alloys of iron and nickel prepared by powder metallurgy technique. PROCEDURE Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, 0.001 5 ; lead, 0.035; tin, 0.025 ; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A representative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 3 2 5-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the surfaces of the particles. The reduced powders, slightly caked, were ground in a mortar and screened again through a 325- mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hydraulic presses. The pellets were compacted in a cylindrical die, ½ in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specifed for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By A. D. LeClaire

This paper claims to provide a description of diffusion processes in solids which is said to be a reformulation of Fick's Laws and therefore, presumably, is supposed to be as general as those laws. In fact, it appears to provide no more than an atomic model of a rather restricted type leading even to results in conflict with experiment. The restriction lies in the assumption, carried throughout the paper, that even in a chemical gradient the jump frequency i of an atom of species i is a function only of the composition on the plane from which it jumps, i.e., ?i = ?i(cl, c2 ...). This means that atom jumps in opposite directions from a site would occur with equal probability. There would then be no tendency for atoms to migrate preferentially in one direction along the gradient, so the model is incapable of accommodating the well established phenomenon of atom drift in a chemical gradient.10-" A more general model that does not suffer this difficulty was discussed in a paper13 I wrote in 1958, and the results therein already contain as a special case those given by Dr. DeHoff. The simplest sufficiently general assumption is to suppose that ?i is a function ?i(a1 a2,...; wl, w2, ..-) of the concentration aj and ? ?j at the site from which and to which, respectively, a jump is made. Any such function can always be expressed as a function of the sum and difference of its arguments. Thus d is the jump distance and g a geometrical constant. Obviously this is zero, i.e., no drift, if ??ri/??j = 0. X is written in this form, revealing two components of the total drift, because it can be shown that only the second component, depending on ??'i/???(?j -aj), actually contributes to the net diffusion flux Ji. This component can be shown,13 by a straightforward ther-modynamic transcription, to be responsible for the so called "thermodynamic factor" in the Darken approximation for a chemical diffusion coefficient is the activity coefficient of i. Because the jump rate ?i in DeHoff's approximation has no dependence on the concentration gradient it does not seem possible to derive the Darken equation from his Eq. [6] without the further rather arbitrary assumption that ?i = const ri. It is to be noted too that the author's derivation of Eq. [12] is only valid when ?i is in fact a function only of the cj at the plane from which the atom jumps—for only then is ci?i a unique function of position and therefore of A. Author's Reply R. T. DeHoff I am indebted to Dr. LeClaire for his penetrating discussion of my paper, "A Reformulation of Fick's First Law". I concede that it does appear initially that the relationship presented in my paper could be derived from the detail atomic model of random walk and atom drift presented in Dr. LeClaire's approach. However, there are some important differences in concept and viewpoint which deserve further amplification. Dr. LeClaire's description is penetrating, detailed, and fundamental. His approach describes an extremely complex phenomenon, the displacement of atoms in a multicomponent gradient, at a sophisticated level. For precisely these reasons, his analysis has not proved to be useful for experimental studies that have practical objectives. For example, in order to obtain the information required to complete the analysis of the jump frequency distribution in a ternary system, the following series of experiments would, I believe, be required: 1) chemical (gradient) experiments, covering the composition range;

Jan 1, 1970

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

C. D. Demond, Anaconda, Mont. (communication to the Secretary*) :—In order to throw some light on this interesting subject, a series of experiments were made with strips of mild steel, containing about 0.14 per cent. of C and 0.22 per cent. of Ma. These strips were thoroughly cleaned and brightened before use, salts were added to distilled water until it corresponded as nearly as possible to the analysis given by Mr. Lee, and in this water at different temperatures were placed four strips of steel; while four other strips, at corresponding temperatures, were placed in the water used at the Washoe Reduction Works. The latter plant has had no trouble from corrosion of furnace-jackets, pipe-lines or boilers. The analysis of the water used at the Washoe works is: Grains er U. S. Gallon. CaCO3........... 2.92 CaSO3........... 0.76 MgCI3........... 0.64 MgCO3........... 0.58 A1203........... 0.12 Fe2O3........... 0.12 SiO2........... 0.58 NaCl........... 0.35 Organic matter, etc.,........ 1.16 7.23 This water is neutral to litmus; while the artificial Copper Queen water was very slightly alkaline, which Mr. Lee informs us is also true of the water at Douglas. Both waters mere well aerated by pouring from beaker to beaker, and by blowing in air from the experimenter's lungs. The results of these tests, given in Table I., show that there is no significant difference between the effects of the two waters.

Jan 1, 1909

By D. J. Carney, R. L. Stephenson

M. O. Holowaty (Inland Steel Co., Chicago)—Messrs. Stephenson and Carney should be commended on the presentation of this very interesting paper. They have introduced new ideas on sampling of sinter and have thereby made a valuable contribution to the qualitative evaluation of sinter. The paper undoubtedly presents a novel approach to the problem of sinter sampling and this is to be regarded as its main value. Sampling of sinter from the pallets prior to the discharge is by no means new. This sampling procedure was used in the past by Philbrook; Hamilton and Ameen and others. The sampling basket used by the authors of this paper, however, permits one actually to obtain a good sample of the sintering mixture. The basket which can also be described as a removable pallet goes then through the entire process of sintering and thus offers a sample which is positively representative of the batch in question. The authors' method of evaluating physical properties of sinter seems to be not altogether clear, however. It is felt that the following points should be clarified: I—In the section describing the shatter test the authors state that a 5-lb sample was used in the actual tests. There is no mention of the initial size of sinter particles used and the method of obtaining this 5-lb sample from the sinter cake weighing about 100 to 120 lb. It is also surprising that the sample was dropped from a height of 3 ft instead of the conventionally used 6 ft. Unfortunately there is no mention of the number of drops to which the sample was subjected. 2—The tumbler test used by Messrs. Stephenson and Carney in testing the samples of iron ore sinter was performed in a standard ASTM coke tumbling drum. The drum measures 3 ft in diam and is equipped with two 3-in. lifter bars. The distance of fall in this testing drum is identical with the distance used in the previously described shatter test. The number of drops in the tumbling drum is approximately double the number of revolutions. The basic difference then between the drop-shatter test used by Stephenson and Carney and the tumbling test seems to be the number of drops to which the sample is subjected and the abrasive action to which the sinter particles are exposed in the rotating drum. In any case, the choice between the shatter test and the tumbler test seems to be only a matter of taste and convenience. 3—The authors of the paper state that "in order to insure getting results that were representative . . . the entire sample obtained by means of the sampling basket was used as the starting material for the tumbler test. If the sample broke in pieces, all the pieces were used regardless of their size." The initial size of the material is known to be a very important factor, influencing seriously the final size of the particles. This should be particularly important in case of hard sinters. It seems also very troublesome and inconvenient to charge 12-in. cubes of sinter weighing about 100 lb into the testing drum. This could be eliminated by taking a standard fraction of somewhat smaller particles.

Jan 1, 1954

By W. C. Muehlhof, L. D. Lamont

THROUGHOUT the anthracite industry's history, the problem of handling and dis¬posing of refuse material has been one of major importance. In the early days of the industry's activities, only the large sizes of anthracite were satisfactory for market requirements and the smaller sizes were deposited as refuse. As time went by, more efficient coal-burning equipment was developed and a market demand was created for the finer sizes of coal. This demand made it possible to recover market¬able coal from banks deposited as refuse in the earlier days of mining. The same condition holds good today and we can see a definite trend toward the objective of utilizing the No. 4 and No. 5 buckwheat sizes. Under present conditions, we know that a limited market exists for No. 4 and 5 buckwheat; we know that the finer sizes of anthracite can be burned as pulverized fuel; we know that these fine sizes can be processed and sold as bri¬quettes, and we also know that the heat content of these fine sizes of coal is compar¬able with that of the sizes now merchan¬dized. Therefore, it should be the objective of the industry to conserve these fine sizes of coal in such manner that if and when processing facilities are developed, and market demands exist, the material can be salvaged and made available to meet these demands. From the standpoint of economical future reclamation, the ideal method of disposing of refuse containing the finer sizes of coal is to deposit it in banks separate and apart from other breaker refuse. By this procedure, the minimum amount of material will be processed in future salvage operations to recover the No. 4 and No. 5 buckwheat sizes. Many collieries in the anthracite region are operated under leases that have a specific term. These lease agreements provide that, upon expiration of the lease by term, exhaustion or otherwise, the ownership of the refuse material reverts to the lessor. Therefore, a question was raised in the minds of these operators: Why should I assume the expense of such pro¬cedure when I have no assurance that I will benefit by the future processing and sale of these fine sizes? Under present conditions, the answer to this question is not one of choice but of necessity, as restrictions imposed by legislation make it mandatory on operators of preparation plants to take necessary steps to properly treat silt-laden waters before permitting them to enter the streams. By reason of these restrictions, the disposal of fine sizes becomes a secondary_ rather than a primary operating con sideration, and the procedure for disposing of this refuse becomes a matter of choice governed principally by topographical and geographical conditions. METHODS OF HANDLING REFUSE There are three principal methods of handling and disposing of fine-size refuse; namely :

Jan 1, 1946

No. Place Date Vol. 1. Wilkes-Barre, Pa May, '71 1 2. Bethlehem. Pa Aug., '71 1 3. Troy, N. Y Nov.,'71 1 4. Philadelphia, Pa Feb., '72 5. New York, N. Y.* May, '72 8. Pittsburgh, Pa Oct., '72 7. Boston, Mass Feb., '73 8. Philadelphia, Pa.* May, '73 9. Easton, Pa Oct.. '73 10. New York, N. Y.Feb., '74 11. St. Louis, Mo.* May, '74 12. Hazleton. Pa Oct., '74 13. New Haven, Conn Feb., '75 14. Dover, N. J.* May, '75 15. Cleveland, O Oct., '75

Jan 1, 1929

By Jack White, Ralph B. Adair

The Mufulira mine in Northern Rhodesia is 13° south of the Equator and at an altitude of 4100 ft above sea level. The concentrator was planned in 1930 to treat about 10,000 tons of ore per day, but before construction work had gone very far the size of the plant was reduced to 1500 tons daily capacity. Then just as the construction was finished in December 1931, the price of copper did not warrant the commencement of operations and it was not until October 1933 that the mine re-opened. Extensions have been made to the plant in 1934, 1935, 1936, 1937, 1940 and finally in 1945. The capacity of the plant when the 1945 extension is completed will be 9500 short tons per day. The various extensions have been carried out with the minimum confusion and with great skill on the part of the designers and the erection engineers. In dealing with the plant in this paper it is proposed to give an outline of the present practice and only to refer to past practice when it is considered of particular interest. Ore Treated The ore consists of fine grained highly siliceous, felspathic and argillaceous quartz- ites, the latter containing graphitic carbon and locally termed graywacke. These rocks are considerably altered near the surface and on the fringes of the ore body. Despite extensive efforts at mixing, both underground and in the crushing plant, many sudden changes of ore take place in the mill feed. The minerals are chalcocite, bornite and chalcopyrite with relatively unimportant amounts of malachite, native copper, azurite, covellite and chrysocolla. Gold is present at about I oz to a thousand tons, and silver at about 2 dwt. per ton. With increasing depth the nonsulphide content or,, as commonly termed locally, the oxide content of the ore is decreasing and is now less than 0.25 pct against a high of 0.77 pct- Crushing Operations The first stage of crushing is done under. ground where the oversize from I2-in. grizzlies is fed to a 56 X 72-in. jaw crusher. At the Selkirk shaft two 10-ton skips deliver the run of mine ore at a rate of 450 tons per hour to the 400-ton capacity shaft bins. One 6 ft wide Ross chain feeder and one locally made air-operated finger feeder feed the two 30-in. McCully crushers. Ahead of each crusher is a 6 X 9-ft spring grizzley spaced at 5 in. on a 35O slope. Neither the Ross chain feeder nor the finger feeder is entirely satisfactory and for the wet, muddy and sticky ore that has to be handled it is planned to replace these with two 6-ft wide apron pan feeders. The McCully crushers deliver a minus 5-in. product, at a.rate of over 500 tons per

Jan 1, 1949

By M. C. Udy, P. C. Rosenthal

THE use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace, The present study presents the results of a systematic survey of. the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels, Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. EXPERIMENTAL WORK Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. [ ] Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions . was prepared with boron additions in amounts of 0.0015, 0.003, and o,006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two com¬mercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120, Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel scrap were used for melting stock. Deoxidation was carried out in the furnace with o.10 per cent aluminum. The aluminum addition was

Jan 1, 1946

A. A. CENTER*—This paper reminds me of the beginning of the work of the Electrolytic Zinc Company of Australasia. Early work for this Company, as some of you may know, was done at the Bully Hill Plant in California. After working there for some time Herbert Gepp, now Sir Herbert, came to the Anaconda Co. plants in Montana where I met him. He spent some months there, in fact almost a year if I remember rightly. That was when we were breaking in the new electrolytic zinc plant at Great Falls, Montana. From there he went back to Australia and started in on the plant there. I believe they had an original plant of about 20 tons per day of cathode zinc. We heard from them for some time, until they were able to go along on their own, and they have done very well ever since as you have heard. Their practice, (the flow sheet, the leaching practice), has been quite different as reported in the paper and apparently they are still following that practice to some extent. While the earliest work on selective flotation was done down in Australia, the big companies there, strange to say, were far behind the American companies in taking it up; and it is only in comparatively recent years they have gone to the alkaline circuit and dropped out thereby more of their iron and lead. The zinc plant now is up to a capacity of 100,000 tons a year and I believe that may be notched up to about 105,000. T. H. WELDON*—I would like to ask

Jan 1, 1950

By S. W. Ross

A. A. CENTER*—This paper reminds me of the beginning of the work of the Electrolytic Zinc Company of Australasia. Early work for this Company, as some of you may know, was done at the Bully Hill Plant in California. After working there for some time Herbert Gepp, now Sir Herbert, came to the Anaconda Co. plants in Montana where I met him. He spent some months there, in fact almost a year if I remember rightly. That was when we were breaking in the new electrolytic zinc plant at Great Falls, Montana. From there he went back to Australia and started in on the plant there. I believe they had an original plant of about 20 tons per day of cathode zinc. We heard from them for some time, until they were able to go along on their own, and they have done very well ever since as you have heard. Their practice, (the flow sheet, the leaching practice), has been quite different as reported in the paper and apparently they are still following that practice to some extent. While the earliest work on selective flotation was done down in Australia, the big companies there, strange to say, were far behind the American companies in taking it up; and it is only in comparatively recent years they have gone to the alkaline circuit and dropped out thereby more of their iron and lead. The zinc plant now is up to a capacity of 100,000 tons a year and I believe that may be notched up to about 105,000. T. H. WELDON*—I would like to ask

Jan 1, 1950

By J. Chipman, N. J. Grant, H. L. Bishop, H. N. Lander

Data of several studies on the equilibrium between molten iron and open hearth-type slags have been combined to determine some of the chemical reactions involved in steel-making. Effects of slag composition and temperature on the iron oxide activity, distribution of sulfur between slag and metal, and the carbon content of the metal are discussed. Also, an overall reaction for the equilibrium between sulfur and oxygen is presented. DURING the past 15 years, a number of significant equilibrium studies have been carried out between liquid iron and simple basic and acid slags in an effort to throw light on the chemical reactions involved in steelmaking. This paper is a summary of the experimental reports on investigations which have been conducted at the Massachusetts Institute of Technology, and of related work in other laboratories. The investigations summarized in this paper include the works of Fetters and Chipman1 and Taylor and Chipman,' which dealt with simple slags that are similar to those found in the open hearth. The sulfur determinations of the slag-metal tests of Fetters and Chipman as reported by Grant and Chip-man" are included. Also, the investigations by Win-kler and Chipman' and Grant and ChipmanQ f more complex slag systems are included in this summary. The experimental procedure is described in detail in each of these papers and will not be discussed. Since the previous reports have been somewhat independent, it is desirable to review and combine the data of the various investigations to determine, as accurately as possible, the reactions in the slag-metal systems of the open hearth. It is the object of this report to present the combined data in such a way as to enhance their utility and applicability. Oxidizing Power of Slags of the System (CaO+MgO)-Si0,-FeO in Equilibrium with Carbon-Free lron The slags selected to determine the iron oxide activity in equilibrium with pure liquid iron were those containing less than 2 pct each of P,O,, MnO, or A1,0, on a weight percentage basis. The method used to calculate activities of iron oxide in liquid slags was that developed by Taylor and Chipman.' The solubility of oxygen in molten carbon-free iron under pure iron oxide slags can be expressed by the following eauation —6320 log (pctO)-------------— + 2.734 [1] where T is the absolute temperature. The oxygen solubility values as determined from Eq. 1 were used throughout this study to calculate the iron oxide activity. The iron oxide activities of slags of various iron oxide contents are plotted in Fig. 1 as a function of the basicity, which is defined as the ratio (pct CaO + pct MgO)/pct SiO,, and are based on molecular percentage values of the components. The percent (FeO), is the total iron content in the slag calculated to FeO. Fig. 1 shows that as the basicity increases at constant mol pct (FeO),, the iron oxide activity increases rapidly and reaches a plateau which extends on the basicity scale from about 1.3 to 2.3; the iron oxide activity then decreases rapidly until a basicity of about 3.0 is reached, where it tends to level off. The solid portions of the curves represent the experimental data of Fetters and Chipman and Win-kler and Chipman. Their experimental heats were made in magnesia crucibles, and hence the slags were saturated with magnesia. The broken lines on the left represent the experimental data of Taylor and Chipman, who used a rotating crucible. In general, these slags contained less than 3 pct MgO. The absence of data for slags containing less than about 40 mol pct (FeO), and basicity ratios greater than about 2.5 made it necessary to calculate curves using ionic concepts of slags. The broken lines on the right, which disregard the solubility limits of di and tricalcium silicate and lime, were obtained by following the treatment of Flood and Grjotheim,"

Jan 1, 1957

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By A. A. Berk

LAGGING technology and the slow spread of information have been the chief obstacles to widespread participation in minimizing the industrial pollution load. These obstacles can be conquered by fact finding and applied research. There are three aspects to the problem of water-borne mineral waste: to minimize the amount being thrown away, to select a predisposal treatment, and to use the products or dispose of them. It is often possible to minimize the waste by making very minor changes in the process that produces it. For example, a manufacturer of automobile bumpers greatly reduced the dragout 'from a plating bath by modifying the design and position of two boltholes.' A plater of automobile hubcaps installed a drainage bar and decreased the loss of chrome-plating solution to the rinse water by about 80 pct.' The mill at a western mine found it possible to discard 60 to 70 pct of an ore with minimum treatment," so that the processing effort could be concentrated on a high-graded slime, with significant reduction in costs and improvement in recovery. The possibilities for waste reduction through process changes are limited only by the imagination. A recent patent points out the advantages of using No. 1 fuel oil instead of water in wet-process cement making;& the fuel oil presumably has better properties than water for this purpose and is said to be almost com'pletely recovered or utilized, so that there is no waterborne waste. Recycling to reduce wastes and improve process economy is very well illustrated in vanadium and uranium recoveries from relatively low grade ore. Ores containing 6 pct calcium carbonate were found to give poor vanadium recovery by the salt-roasting process because the vanadium was converted to water-insoluble calcium vanadate. Following the salt-roasting process, sulfuric acid was used to leach the uranium. Enough calcium sulfate was formed

Jan 1, 1958

By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

I would like to congratulate the authors on an interesting paper and, in particular, on their justification of the use of superposition in treating gas wells. They state, however, that no theory has previously been developed lor treating the variable rate drawdown case. In a paper published a few years ago by my colleagues and myself, a method is described which allows a constant rate drawdown curve to be derived for any well. regardless of real rate variations. This method has the great advantage that it is not necessary to make any assumptions regarding the form or uniformity of the reservoir, and the derivation suggested by the present authors is simply an idealized case of our more general treatment. In the light of several years&apos; experience in the derivation of constant rate drawdown curves: I would like to point out that the method proposed by Odeh and Jones may lead to confusing answers, particularly if applied over an appreciable time interval. The reason is that, if pressures are measured when a well is flowing, non-linearities in plots like Figs. 1 and 2 can arise due to either (1) changes in the skin factor with time and/or flow rate, or (2) an inhomogeneous reservoir. Separation of these two effects is only possible if some of the pressures used in the analysis are measured when the well flow rate is 0 or, in other words. during brief shut-in periods. REFERENCES 1. Arthur, K. B.. Metunomski, Z. G. and Ruche, Ms "Intetet ct methode d&apos;utilisa tion des mesures de pression [)our Petude des gisemonts" Revue de T&apos;I.F.P. (Nov., 1962) XVII, 1299. 2. Thomere, R. and Arthur, K. R.: "Analysis of the Pressure Bet~avior of a Production Well Subject to Interterence and Its Application to Reservoir Models", Paper SPE 1189 presented at SPE :Amund Fall Mecting Ireld in Denwer, Colo. (Oct. 3-6, 1965).

Jan 1, 1966

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.&apos;, In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, &apos; The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B&apos;O

Jan 1, 1969