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By Robert H. Weber

INCREASING acceptance of perlite products, chiefly in the fields of lightweight structural aggregates and thermal and acoustic insulation, has led to expanding market demands that have encouraged many new producers to enter the field. In some instances, however, the failure of these producers to anticipate the variable response of perlite to conventional processing methods has led to difficulty in establishing an economical flowsheet by which a predictable specification product could be obtained. It is not the writer's intent to provide a solution to these problems, but rather to summarize their nature. It is to be hoped that members of the industry who have hurdled some of these obstacles will document solutions arising from their experience. In this treatment the term perlite will not be restricted to the petrographic definition but will apply to all volcanic glasses. Expansible obsidians and pitchstones are accordingly included in this broader industrial classification. Chemical Properties: Although perlite has been reported to range in composition from that of rhyolite to that of andesite, it is probable that most of the glasses have the composition of rhyolite. When recalculated to an anhydrous basis, the five analyzed glasses from New Mexico, representing five distinct physical types from widely separated deposits, show an amazingly uniform oxide composition. Water content is the only major compositional variable; total water ranges from a low of 0.37 pct (non-expansible obsidian) to a high of 8.95 pct (expansible pitchstone). The wide range in expansion characteristics exhibited by these samples cannot be related to significant variations in the composition of the nonvolatile fraction and has been only partially correlated with variations in water content.

Jan 1, 1956

By C. Zener

HE present paper has its origin in an attempt A by the author, extending over the last several years, to understand the influence of the magnetic properties of the constituent atoms upon the various properties of metals and alloys. During this study the author has been impressed by the important role which magnetism plays in the many facets of metallurgy. In writing this paper he has attempted to convey to his colleagues some concept as to the role magnetism will play in the future development of metallurgy. In some of the subjects herein discussed, such as the influence of magnetism upon phase boundaries and upon mechanical properties, only general thermodynamical properties associated with ferromagnetism are introduced. For these subjects, it is not anticipated that any serious differences of opinion will be encountered. A discussion of the other subjects requires the adoption of a quite specific model of the magnetic structure of the metal. This model is discussed under "Magnetic Shells and Their Interactions." The simple model adopted in this paper has been criticized' as being mathematically inconsistent. This criticism has been ably silenced by Dr. W. J. Carr' of this laboratory. The simple model adopted in this paper has been criticized as being inconsistent with observations on magnetic structure using neutron diffraction. This apparent discrepancy has been resolved by Bader3 who has shown that the finite velocity of neutrons prevents neutron beams from detecting the anti-ferromagnetic structure of the type predicted by the simple model adopted in this paper. Magnetic Shells and Their Interactions An electronic shell of an atom is specified by two symbols.' The first symbol is a number and denotes the total quantum number of the shell. The second symbol is a letter and denotes the orbital angular momentum of each electron within the shell. The letters s, p, d, f are used to denote an orbital angular momentum of 0, 1, 2, 3, respectively, in units of h/2a, where h is Planck's constant. As we pass from scandium to nickel in the first transition period, we eraduallv fill the 3d shell. This shell is responsible for ferromagnetism and hence may be called the magnetic shell. The component of the orbital angular momentum along some specified direction must be an integral multiple of h/2~. Thus, for a d electron this component can have any one of the values —2, —1, 0, 1, 2 times h/2a. In addition to its orbital angular momentum, each electron has an intrinsic angular momentum, hereafter called spin, due to a rotation about its own axis. This spin can have either of two components + Yz (h/2a) or — Yz (h/2~) along the specified direction. A fundamental principle of atomic structure, known as Pauli's exclusion principle, is that no two electrons in a given shell may have identical components of orbital angular momentum simultaneous with identical components of spin. The 3d shell thus may have at most ten electrons. Since an intrinsic angular momentum of a charged particle is necessarily associated with a magnetic moment, the spin of an electron may be thought of as referring to either this angular momentum or to the associated magnetic moment. The electron configuration of the ground state of the isolated atoms in the first transition row is reproduced in Table I. The superscript represents the number of electrons in each shell. For the purpose of this paper, the most important principle of atomic structure relates to the manner in which electrons are added to a shell as the atomic number is increased. This principle, commonly known as the principle of highest multiplicity or more simply as Hund's rule, states that within a given shell the maximum number of electrons have spins pointing in the same direction as is consistent with Pauli's exclusion principle. An application of this principle to the d shell is illustrated in Fig. 1, where the spin structure is given for shells containing from 1 to 10 electrons. The physical basis of Hund's rule is the exchange energy discussed first by Heisenberg in 1928. This is a coupling between electrons with parallel spins (spins pointing in the same direction), the coupling

Jan 1, 1956

By E. F. Bailey, L. S. Birks

The effect of stress on the austenite to ferrite transformation in carbon steel was studied by X-ray diffraction techniques. Tensile stress was found to cause reorienta-tion of austenite above the transformation temperature, to accelerate equilibrium conditions at the transformation temperature, and to cause precipitation of large carbides at a critical value of stress. IN the past, a number of papers' have discussed the effect of stress on the austenite to martensite transformation at relatively low temperatures. In general, it has been shown that tensile stress induces some transformation at a given temperature, while compressive stress retards the transformation. Very little work has been reported on the effect of stress on the transformation from austenite to ferrite plus carbide near the A, point in steel. One of the few papers in the literature2 reports an increase in A1 of about 1°C in pearlitic steel upon the application of tensile stress. In this paper, the effect of tensile stress on eutec-toid steel at, and above, the A, point was studied in

Jan 1, 1956

By F. V. Lenel

Resistance sintering under pressure is a method of hot pressing in which a powder compact is subjected to pressure and simultaneously heated by passing a low voltage high amperage current through it. Equipment for this process is described. Its basic characteristics such as resistance requirements for powders and compacts, temperature distribution in compacts, and gas reactions during resistance sintering are discussed. Examples of the sintering process in compacts made of a single metal or an alloy powder and in compacts made of mixtures of powders are presented. Potential commercial applications of the process are evaluated. THE usual sequence of operations in commercial powder metallurgy is to compact metal powders in a die at room temperature and sinter the compact subsequently without applying pressure while the compact is in the sintering furnaces. In hot pressing, on the other hand, the compacting and the sintering are combined. The loose powder, or in many cases a cold formed compact, is inserted into the die which is held at the hot pressing temperature, the compact is left in the die until it attains its temperature, and then pressure is applied and maintained for a given length of time. The die may be heated by surrounding it with a suitable furnace, by high frequency induction heating, or by passing current through the die. In hot pressing, compacts of high density and good mechanical properties can be produced in a relatively short time. One of the principal difficulties in hot pressing is the lack of suitable die materials which will have adequate strength at the hot pressing temperature. This difficulty can be overcome at least partially by heating only the material to be hot pressed without heating the die directly. This can be done by passing a low voltage high amperage current through the material and simultaneously subjecting it to pressure. Either loose powders or compacts can be hot pressed by this method in which the desired temperature is produced by the power dissipated in the metal powder. This method of hot pressing has been termed "electrical resistance sintering under pressure." The most significant differences between this operation and conventional hot pressing are: 1—The sintering times are very short, usually a fraction of a second and at most a few seconds. 2—The powder and die are initially cold. 3—Heat is generated within the powder itself and not conducted in from the die. 4— The pressure used is high. 5—Cooling following sintering is rapid, amounting to a quench. Resistance sintering of metal powders under pressure has been suggested repeatedly. In 1933, G. F. Taylor' proposed an apparatus which consisted of an insulating tube made of glass, or a ceramic filled with the powder to be pressed, and plungers above and below the powder. The powder was to be heated by passing an electric current through it and pressure was then applied. The apparatus was intended principally for hot pressing cemented carbides. Although the principle of resistance sintering under pressure is clearly shown in this patent, few details are given. A sintering period of a second or a fraction of a second, which is terminated by the operation of an inertia switch, is mentioned but no values for current density are mentioned. Low pressures, such as atmospheric pressure or a somewhat higher pressure exerted through a lever, are suggested. W. D. Jones' discussed electrical resistance sintering under pressure and proposed using resistance welding apparatus for this purpose. In a patent issued in 1944, G. D. Cremera described a method of electrical resistance sintering under pressure using resistance welding apparatus which was to be applied mostly to nonferrous metals such as copper, brass, bronze, and aluminum. Current densities of 400,000 amp per sq in., sintering times of 1 and 2 cycles of 60 cycle current, and pressures of 5 to 10 tsi are proposed. Cremer suggested using an

Jan 1, 1956

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The mechanical properties of Ti-C and Ti-C-0 alloys can be altered by heat treatments to dissolve or reject carbon from solid solutions. The maximum strength is obtained by annealing just below the peritectoid temperature. Quenching from the ß-carbide field results in softening. Impact behavior is influenced by the extent of solution of interstitials CARBON is not as important in titanium alloys as it was in earlier years when graphite induction melting was more prevalent. With induction melting, carbon pickup is about 0.5 to 0.8 pct. Cold-mold arc melting with graphite electrodes, which is among the more current methods, results in carbon pickup of 0.1 to 0.2 pct. The titanium-sponge melting stock itself contains about 0.02 to 0.07 pct C, picked up from the magnesium used in the reduction process. Thus, carbon is still one of the more important contaminants in titanium and needs careful study and evaluation in order to understand titanium and titanium alloys. Moreover, it is equally proper to consider carbon as an alloying addition because, in controlled amounts in titanium alloys, it may serve a most useful function. This is particularly the case where the ultimate in toughness is not required. The addition of carbon to titanium results in a peritectoid-type system as illustrated in Fig. 1. The solubility of carbon is seen to be higher in the a phase than in the ß phase in the temperature range of interest. Below the peritectoid temperature, the solubility of carbon in a titanium decreases with decreasing temperature. This type of system permits many microstructural and heat-treatment variations which may influence the properties of the alloys. The study of how the microstructure variations affect mechanical properties is described in this paper. Experimental Procedures The experimental techniques and testing methods used in this work were the same as those described in detail in a previous paper.' No further descriptions will be given except where changes have been made. High purity iodide titanium, produced by the New Jersey Zinc Co., was used in all of the alloys. Carbon additions were made using high purity spectro-graphic carbon electrodes in order to obtain the highest purity carbon available. The alloys were prepared by double arc melting to reduce the possibility of segregation. The alloys were forged at 875°C to ¾ in. round, descaled, vacuum annealed for 5 hr at 900°C to remove the residual hydrogen, and swaged to ¼ in. round at 750°C. All heat treatments were made on material in this initial condition. Two of the early Ti-C ingots were found to have been contaminated in melting. Vacuum-fusion analyses showed that the two contaminated alloys had picked up oxygen, so the test results on these two alloys permitted an evaluation of ternary Ti-C-0 alloys. A list of the alloys and their compositions are given in Table I. Properties of Ti-C Alloys In a peritectoid-type system, such as the Ti-C system, the chief microstructural variable which influences the properties is solid-solution strengthening. For a given composition, it is possible to control the disposition of carbon, either in solid solution or as the compound Tic, by suitable heat treatments. When in solid solution, the carbon present in the alloy makes a definite contribution to the strength of the alloy. However, when present as Tic, it has very little effect on the strength. Other microstructural variables considered in this investigation were transformation structures and grain size. As discussed in subsequent sections, these variables have only a minor effect on properties as compared to the solid-solution effect. Solid-Solution Strengthening: The principal strengthening mechanism for Ti-C alloys has been found to be solid-solution strengthening. Carbon in interstitial solid solution strengthens titanium, but has very little strengthening effect if present as the compound. Since carbon has a higher solubility in

Jan 1, 1956

By R. Schuhmann

As a response to rapidly growing specialization in various branches of metallurgy, it is proposed that undergraduate education in metallurgical engineering should be built up around four principal scientific themes: 1—thermodynamics, 2—structure, 3—mechanics, and 4-—rate processes. THE following quotation from a recent article by von Bertalanffyl describes very well the situation which today challenges curriculum designers in all branches of science and engineering: "Modern scientific education is presented with a well known dilemma. The amount of facts in modern science, and in any of its smallest branches, is enormous. Life in general, and the academic curriculum in particular, is short. The abundance of factual data, as well as the intricacy of modern scientific techniques, experimental and theoretical, necessitates utmost specialization. This specialization, unavoidable though it is, involves serious danger for both the education of the scientist and the social function of science. "In so far as the advancement of science is concerned, history shows that interconnection of different fields and problems is a most important basis of progress. Many of the paramount achievements of science arose on borderlines, and from the synthesis of formerly separate fields . . ." Specialization in subfields of metallurgy has become a serious educational problem only in about the last decade. The growth in specialization, almost as a necessity, has paralleled the rapid growth in metallurgical knowledge during this period. Moreover, in planning future educational policies, the educator must be concerned not only with the rate of increase in metallurgical knowledge and with the concomitant rate of increase in specialization, but also with the second derivatives, that is, with the rates of increase of the rates of increase. These second derivatives are positive and large; the growths being dealt with are self-catalyzing, or like a chain reaction. As a measure of specialization, the length of the list of different kinds of metallurgies can be considered, the kinds of metallurgy which represent one person's particular interests and those of other practicing metallurgists. To start with, there are physical metallurgy, process metallurgy, and mineral dressing, then mechanical metallurgy, metal processing, foundry metallurgy, corrosion, solid state physics, high temperature metallurgy, welding, powder metallurgy, nuclear metallurgy, etc. Each of these fields is growing so rapidly that any one metallurgist can hope at best to keep up to date in only one or two. What is the impact of all these "metallurgies" on metallurgical education and metallurgical curricula? In answering this question, it can be said, first, that educators have resisted fairly well the temptations to split up metallurgy, with different curricula, different options, degrees with different labels, and the like—degrees are still given in plain Metallurgy and Metallurgical Engineering. In other ways, though, the pressures of specialization have had noticeable effects. There is a tendency to think of these "metallurgies" as the important subdivisions of Metallurgical Engineering and to work up

Jan 1, 1956

Jan 1, 1956

Institute of Metals Division Iron and Steel Division Extractive Metallurgy Division Council A W Thornton (ISD), Chairman, R W Shearman, Secretary, C S Barrett (IMD), J C Kinnear, Jr (EMD), John Chipman (ISD), J S Smart, Jr (IMD), A W Schlechten (EMD), M E Volin (MED), D S Eppelsheimer (MIED) Journal of Metals Editorial Advisory Committee J S Smart, Jr, Chairman, W A Dean, J J Golden,T D Jones, Evan Just, J C Kinnear, Jr, M Tenenbaum Pacific Northwest Regional Conference E R Marble, General Chairman, Marshall Huntting, Assistant General Chairman, W C Douglass, Mining Chairman, H C Hughes, Mining Chairman for British Columbia, W C Douglass, Mining Chair¬man for United States, Paul Billingsley, Geology Chairman, W D Nesbeitt, Miner¬als Beneficiation Chairman, H D Kelley, Industrial Minerals Chairman, J G Johnston, Metals Chairman, Lloyd Banning, Iron and Steel Chairman, W G Rouillard, Extractive Metallurgy Chairman, E C Roberts, Physical Metallurgy Chairman, D A Pifer, Mineral Industry Education Chairman, Frederick Brien, General Arrangements Chairman Metals Branch Membership Committee C M Squarcy, Chairman, R C Cole, Harold Mar¬golin, M E Nickel, S K Scovil Bylaws Committee A W Thornton, Chairman, W R Hibbard, Jr, J S Smart, Jr (IMD), John Chipman, T S Washburn (ISD), T D Jones, J D Sullivan (EMD)

Jan 1, 1956

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines or phosphate ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pct. When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900" to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956

By H. L. Riley, B. W. Gandrud

AS far as the present writers know, this system of flotation has not been used elsewhere in this country, but in the last couple of years it has been introduced, with minor variations, at one plant in England and one in Wales.' The system has been described and discussed in a number of publications.2-5 The following is quoted from an abstract of the latest of these,5 a paper presented at an International Conference on Industrial Combustion in 1952. On the basis of experience to date with the commercial plants, it is believed that the kerosene-flotation process incorporates all the necessary elements to make it greatly superior to anything else now available for treating of fines in wet processes of coal preparation. Additional study and investigation are still needed, however, to determine if certain phases of the process can be improved to such an extent as to make it generally satisfactory and acceptable to the industry. Further improvements will be needed with respect to the capacities of the flotation cells and the reagent consumption. The situation referred to above explains why an investigation is being made of the possibilities of achieving better cell capacities. Results obtained from this investigation, which is still in progress, are believed significant with regard to both cell capacity in general and the relation of cell design to cell capacity in particular. Commercial equipment now being used in a laboratory-type investigation should have performance characteristics similar to those of the larger machines. Equipment and Procedures: All flotation tests have been made in a standard Denver sub-A 24x24-in. unit cell of 12-cu ft volume. Cell modifications to make it more suitable for the tests were an adjustable front-wall section for varying cell depth and a perforated scraper-drag assembly for removal of the float product. There is also an apron dry-coal feeder, a gravity-feed water supply, reagent feeders, and a centrifugal pump that feeds the mixture of coal, water, and reagents into the flotation cell. A wattmeter connected into the drive-motor circuit records the power requirements of the impeller throughout each run. Dry coal, water, and reagents are all fed through a pan-type intake to the feed pump. A Sturtevant blower was set up to furnish air for supercharging. A centrifugal pump with a garbage-can intake provides for disposal of refuse flow to an outside settling tank. Figs. 1 and 2 show the flotation cell; Fig. 2 also illustrates the blower for supercharging. For purposes of this investigation, the percentage by weight of the feed coal recovered in the float product under a standard set of conditions has been considered as the criterion of cell capacity. The authors realize that such a criterion may be somewhat unorthodox, as the term cell capacity is usually understood to refer to feed input and ordinarily takes into account the ash analyses of the float product and refuse. However, the word capacity is flexible enough so that Webster gives one definition as maximum output, a definition which seems to justify, at least partly, acceptance of the above criterion. It has been the authors' experience in the Birmingham district that the ash-reduction efficiency of the coal-flotation process is generally satisfactory and that the only real problem is to increase the rate of float recovery so that the feed rate to any given bank of cells can be increased without undue loss of coal in the refuse. Originally it was planned to operate the flotation cell to simulate continuous operation during sampling periods. It was assumed that operating for reasonable time with feed coal, water, and reagents turned on would stabilize conditions so that the weight of float coal discharged during a fixed time interval would be an accurate measure of the rate at which the coal was being floated. It developed, however, that this supposition was erroneous. The float coal, caught for fixed time intervals and weighed, gave widely varying results in duplicate runs. Efforts to correct this trouble failed, and it was decided to try to operate on a batch-test basis, whereby all the float coal produced during a run on a known weight of feed coal would be caught in tubs, dewatered, and weighed. This method gives consistent and reproducible results, with total float product weight rarely varying by more than 3 or 4 pct on duplicate runs. The standard test procedure is as follows: A 132-lb sample of dry feed coal is weighed and placed in the feed hopper. The feeder is adjusted for a rate of 800 lb per hr. Feed water and reagents are turned on, and the feed and refuse pumps are started. One minute later the impeller is started. Six minutes are allowed for the cell to fill up with the water-reagent mixture. The feed of dry coal is started at the end of this 6-min period. One minute later the float-coal removal drag is started. The float coal is caught in one tub for the first 6 min after the flow of feed coal starts. Tubs are then changed, and the float coal is caught in a second tub until the feed coal runs out, when the tubs are again interchanged to catch the float coal for the remainder of the run in the first tub. The cell is kept running for 3 min with the water and reagents on after the feed stops to allow residual float coal to be removed. At the end of a test the wet float coal in both tubs is weighed and the total weight recorded. The product in the second tub is used for moisture determination and screen-size analyses. When the

Jan 1, 1956

By P. R. Sperry

Aluminum alloy 3S was examined to determine the relationship between the applicable phase diagram and the microstructures produced under conditions tending toward non-equilibrium as well as equilibrium. The only phases present in the alloy were aluminum, (Mn,Fe)A16, aAI(Mn,Fe)Si, and silicon. It was found that the alloy behaved essentially as though it belonged to the Al-Mn-Si system. The effects of various solidification rates and of various homogenization treatments were studied. Particular attention was given to a nonuniform precipitate distribution which reflected the solute distribution in the cast aluminum solid solution. Some possible explanations for the solute distribution based on characteristics of the Al-Mn-Si or AI-Mn systems were discussed. ALUMINUM alloy 3s (aluminum plus 1.25 pct Mn) is one of the oldest and the most widely used of the wrought aluminum alloys. In spite of this fact, there are some aspects of the metallography of 3s which have not been revealed or which have not been brought to the attention of the metallurgist working with the alloy. The purpose of this investigation was to demonstrate in general how some of the fundamentals of equilibrium phase diagrams may be applied to the study of an alloy and to show specifically the origin of certain metal-lographic features of aluminum alloy 3s. It is hoped that this information can serve as a basis for solving specific problems relating microstructure to such things as mechanical properties, recrystallization, grain growth, and surface finish. Literature Survey Considering that alloy 3s contains only one alloying addition, manganese, it seems reasonable that it would have characteristics pertaining to the A1-Mn system. However, those characteristics might well be altered by the impurities in the commercial alloy, especially iron and silicon. Therefore, not only the simple binary but also more complex systems had to be reviewed. One characteristic of the A1-Mn system worthy of mention is its sluggishness, which leads to conflicting solubility data1,'2 and makes it relatively easy to supersaturate the solid solution and shift the eutectic composition during rapid solidification.3'4 Another characteristic is the strong influence which small amounts of impurities, especially iron, exert in lowering the solid solubility of manganese. Undissolved manganese is ordinarily present in an intermetallic phase, MnAl,, having an orthorhombic crystal structure. A metastable precipitating phase designated as "G" has been reported but small amounts of iron and silicon suppress this phase entirely." Raynor has established that MnA1, can dissolve a considerable amount of iron by a substitution of iron for manganese atoms up to 50 atomic pct.'" Consequently, in the Al-Mn-Fe liquidus diagram, the eutectic valley separating the primary aluminum and (Mn,Fe)Al, fields is fairly close to a constant Mn + Fe content." This is an important consideration in regulating the composition of 3s and also other aluminum alloys with high manganese additions."

Jan 1, 1956

By J. D. Sudbury, J. E. Landers, D. A. Shock

The external corrosion of casing is one of the most important problems facing the present day production man. A 1953 NACE report' estimated the annual cost of casing corrosion at $2,200,000 in 22 fields studied. The fields represented only 10 per cent of the wells in the United States. It was significant that 77 per cent of the failures reported were due to external corrosion. A variety of means for combatting the casing corrosion problem have been discussed in papers such as the NACE survey' mentioned previously. No attempt to revicw these will be made in this paper. Thc scope of this paper has been limited to a discussion of the following major items: (I) an instrument for studying external electrolytic corrosion; (2) use of this instrument to determine the quantity of protective current required to prevent corrosion of casing; and (3) problem of accelerated external corrosion of the oil string at the base of the surface string. ELECTROCHEMICAL MECHANISM OF CORROSION It IS gcncrally belleved that one major cause of external corrosion is the existence of electrolytic cells operating between various formation waters. A theoretical discussion of the role of earth potentials in casing corrosion has been presented by L. de Witte and F. J. Radd.2 A brief picture of the electrolytic corrosion action between two differcnt formations (A and B) is presented in Fig. I. This picture is a review to many but is given to insure clarity. In the anode area, oxidation takes place as iron ions go into solution in formation A as a product of corrosion. In the cathode area. reduction takes place and hydrogen atoms are formed at the boundary between the pipe and formation B. The flow of electrons. as indicated. is into the pipe at the anode or corroding area and out of the pipe into the formation at the cathode. In order to conform with regulations of this journal, the flow of a conventional current (I! is also indicated in this sketch. All subsequent references will be to this so-called conventional current flow and will be indicated by the symbol (I). As this action takes place the layer of hydrogen developed on the cathode offers a resistance to the flow of current in the cell. It is said (hat the cathode has been polarized. This polarizing film can be rcmoved by addition of a so-called dcpolarizing agent which reacts with and removes this hydrogen film. Such an agent must be present in ordcr for this corrosion reaction to go at a rate sufficient to cause a severe corrosion problem. The two common depolarizing agents are: (I) oxy-sen. which readily reacts with hydro gen to form water, and (2) certain bacteria which use atomic hydrogen as part of their life process. It is not difficult to explain the presence of these agents. Oxygen may be present in some very shallow formations. Sulfate reducing bacteria are found to exist in nearly any ground where mud pits might be dug. THE CASING POTENTIAl-PROFILE Instrumentation A sketch of the equipment* uscd in determining casing potential profiles is shown in Fig. 2. The tool is run in the hole using a hoist truck with a three-conductor cable. This tool must be run with tubing and rods out of the hole and should be run with the flow line disconnected. By proper choice of electrode size it can be run in any size casing. The electrodes must be run in an open hole or a hole filled with oil. Measurements cannot be made while immersed in water. The tungsten carbide-tipped knives serve as the electrical robes and arc spaced 25 ft apart. The potential difference along a 25-ft section of casing is measured with a potentinmeter to an accuracy of about 5 mv. Current flowing in the pipe can then

Jan 1, 1956

By J. R. Low, M. B. Reynolds, L. O. Sullivan

The effect of neutron bombardment upon the stability of type 347 austenitic stainless steel has been investigated by a magnetic technique. The relation of the ferrite content of a stainless steel to its magnetic properties is given, and an apparatus suitable for the measurement of the ferromagnetic saturation induction of small specimens is described. Results of measurements on irradiated specimens are tabulated. Exposure to a neutron flux was found to cause a slight increase in the ferrite content of type 347 stainless steel, the change increasing with increasing length of exposure and with increasing initial ferrite content. The similarity of the effect of irradiation to the effect of annealing is pointed out. Possible effect of irradiation upon density of austenitic stainless steel is discussed. COMMERCIAL austenitic stainless steels are alloys of iron, chromium, and nickel, plus small quantities of other elements. Although these alloys are normally used in the austenitic condition, this state is thermodynamically metastable at ordinary temperatures and transformation to a more stable state takes place under favorable conditions. In the austenitic state, these stainless steels have the face-centered-cubic crystal structure characteristic of y iron, but the stable state at room temperature is a mixture of austenite and body-centered-cubic ferrite. The transformation from the pure austenitic condition may be brought about by cold working the alloy at a temperature below that at which the aus- tenite becomes thermodynamically unstable (about 400°C), the completeness of transformation increasing with increasing severity of cold work and decreasing temperature. The behavior of the austenitic stainless steels under ordinary conditions of use is rather well known. However, use of these alloys in a nuclear reactor introduces a new variable: the effect of neutron bombardment upon the transformation from the austenitic to the ferritic state. It was with this in mind that a study of the radiation stability of austenitic type 347 stainless steel was undertaken. Magnetic Technique for Ferrite Determination Commercial austenitic stainless steels such as type 347 undergo little transformation under normal conditions of fabrication and use. In view of this fact, it seemed likely that neutron irradiation would change the ferrite content of the alloy but little. The method chosen for measurement of the effect of neutron irradiation was thus limited to one which would be quite sensitive to small changes in the ferrite content of the alloy. Of the properties of the stainless steel which can be measured, the magnetic characteristics are most sensitive to the quantity of ferrite present.

Jan 1, 1956

By P. Farrar, H. Margolin

The Ti-Pb diagram was investigated in the region 0 to 58 pct Pb and from 500°C to liquidus temperatures. Three reactions were encountered: I—ß?a+Ti Pb at 725 10°C; 2—ß+L?Ti4Pb at 1305+ 10°C; and 3—the possible eutectic L-+Ti,Pb and y between 1200" and 1300°C. LEAD-RICH alloys have been investigated by Nowotny and Pesl,' who used sintered compacts and studied the region from 37.5 to 100 pct Pb by X-ray diffraction analysis. The only phase found in addition to titanium and lead was the hexagonal compound Ti Pb. Alloy systems of lead with metals of the transition group, such as iron, chromium, tungsten, cobalt, nickel, or manganese, generally show little liquid or solid solubility.' Craighead et al.,3 however, indicated that lead is soluble in a and ß titanium to at least 2.1 pct. They also found that approximately 50 pct of the lead added was lost during the arc-melting of Ti-Pb alloys. In the present investigation, are-melting also was used to prepare Ti-Pb alloys and similarly large lead losses were encountered. Experimental Procedure Alloy Preparation: Considerable difficulty was encountered in the melting of the Ti-Pb alloys and a number of experiments were performed before the method described was developed. Alternate layers of lead and titanium were wrapped with titanium sheet and compacted. This "sandwich" was annealed at 300" to 350 °C and was melted according to the procedure described by Cadoff and Nielsen.' Using a low current, 150 amp, and an argon atmosphere, four to eight 10 to 20 sec melts were made on each alloy, with the button being turned over between each melt to insure homogeneity. In the high lead range, the preliminary sintering was found to be of doubtful value and was eliminated. In the region above the nominal composition of 70 wt pct Pb, the alloys prepared in this manner always consolidated into two phases. The outside appeared to be composed entirely of lead and the inside was a Ti-Pb alloy. In order to determine whether this phenomenon was caused by a miscibility gap, master alloys with a nominal composition of 40 wt pct Pb were machined and mixed with various percentages of lead sheet. This mixture was compacted and melted in the same manner as the other alloys. Although these alloys were not homogeneous, they did not show the layering that was observed

Jan 1, 1956

By Robert U. King, John W. Vanderwilt

THE Climax molybdenite deposit in Lake County 100 miles southwest of Denver is located in the central part of the mineral belt extending northeasterly across the state. Principal geographic features and geology are shown on Fig. 1. The first period of molybdenite mining, which began in 1918, ended in April 1919 because of limited demand and a price drop to about 72¢ per lb. During this time the ore came from the Leal level and surface outcrops at a higher elevation. Rate of mining was 250 tpd and several million tons of ore averaging 0.7 pct molybdenite were developed. Since April 1924, when the second period* began, Climax Molybdenum Co. has been the only operating company. Production in 1924 was 400 tpd and finding ore was a continual problem. When the White tunnel was extended, however, further ore was encountered. The orebody was thought to be tabular until 1926, when B. S. Butler recognized the relation of the developed ore on the Leal and White levels to a central area of fine-grained hydrother-mal quartz, and by 1929 diamond drilling had blocked out indicated ore reserves in excess of 100 million tons. In 1946, on the basis of information obtained from 25 miles of mine workings and a completed exploratory program involving over 200,000 ft of diamond drilling, the present authors reviewed and brought up to date the geology of the orebody. More recently Sears," employing microscopic techniques, made a study of hydrothermal alteration and mineralization, and Howell and Schassberger'" restudied available geologic data. Production (1953) of molybdenite ore has been expanded to over 25,000 tpd and total production from 1918 through 1953 has been: Tungsten, tin, and pyrite are byproducts and monazite also was produced from 1949 through 1951, after which it was not saved. A maximum of 15 to 20 tons of monazite was produced. Geology of the Area Pre-Cambrian crystalline rocks constitute most of the Mosquito Range for several miles to the north, east, and south of the Climax molybdenite deposit, see Fig. 1. To the west the crystalline rocks are in fault contact with shales and sandstones of Pennsyl-vanian age. Both crystalline rocks and sediments are intruded by dikes and sills of Tertiary age. Numerous faults with small displacements are to be found in the crystalline rocks east of the Mosquito fault and in the sedimentary beds to the west. Pre-Cambrian Rocks: The pre-Cambrian rocks consist of schist and gneiss, identified with the Idaho Springs formation, and granite with minor pegmatite correlated with the Silver Plume granite of the Silver Plume area. The Idaho Springs formation is a general term applied to pre-Cambrian schist and gneiss found over a large part of the Colorado Front Range. At Climax this formation consists largely of biotite-schist and quartz-biotite gneiss with minor quantities of plagioclase and orthoclase, although in places appreciable quantities of feldspar and quartz are present in the more gneissic varieties. Locally, especially along the contact with granite, recrystal-lization of the schist has produced coarser texture and a more pronounced than average gneissic appearance. The gneiss and schist have been mapped as a single unit by Butler and Vanderwilt (1933)" and by Singewald (1951).12 Schist predominates at the higher elevations of the Mosquito Range and in the area to the north and east of Climax. The regional trend of schistosity is northeast with varying dips to the east. Silver Plume granite and associated pegmatite intrudes the Idaho Springs formation. Silver Plume granite in many places and in the Climax district in particular has an irregular form, and many large and small inclusions of schist and gneiss occur within the granite. Granite predominates at the surface in the immediate vicinity of the area of hydrothermal alteration and extends for several miles to the northeast and southeast. As more schist is present at lower levels of the mine than in the upper levels, the suggestion is that the granite is sill-like in form,

Jan 1, 1956

By Jim Douglas, H. H. Rachford, D. W. Peaceman

The problem of unsteady-state gas flow through porous media has been solved numerically only for the case of linear or radially symmetric reservoirs. A recently introduced numerical method for solving the unsteady-state heat flow equation in two dimensions is applied to the calculation of the depletion of a square region containing a perfect gas. Solutions are presented in graphical form for various values of dimensionless parameters. The solutions are compared with published .solutions for radial reservoirs. I NTR ODUCTION The problem of unsteady-state flow of gas through porous media gives rise to a second-order non-linear partial differential equation for which no analytical solution has been found. Numerical approximations to solutions of the gas flow problem have been obtained by the stepwise solution of an associated difference equation1,2. However, the methods so far developed have required that the reservoir be either linear or radially symmetric. This restriction in shape has been necessary so that only two independent variables be considered, namely, one distance variable and time. In order to deal with reservoirs having more realistic shapes, it is necessary to develop numerical procedures for the solution of the gas flow problem involving two distance variables. A numerical procedure, denoted as the alternating-direction implicit method, for the solution of the heat-flow problem in two dimensions has recently been introduced" By the use of this procedure, approximate solutions have been obtained for heat-flow problems in a square8, and in regions having various non-rectangular boundariesa. Because of the similarity between the equation for heat conduction in solids and the equation for gas flow in porous media, it is reasonable to expect that the alternating-direction implicit method should also be useful for solving the gas flow problem in various two-dimensional regions. Solutions have been calculated for the simplest two-dimensional region, a square reservoir with a single well in the center. While reservoirs of such simple geometry seldom, if ever, exist, the solution of this problem is of some practical importance because it is also the solution of another problem, that of determining the depletion history about an individual well in an infinite uniform reservoir containing wells spaced throughout on a square lattice and producing equally from each well. Finally, it is of interest to compare solutions for a square reservoir with those for a circular reservoir and to determine the effect of the shape of the boundary for that particular case. METHOD OF CALCULATION Basic Differential Equation By combining the equation of continuity, the perfect gas law,

Jan 1, 1956

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto' proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer's analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956

By J. D. Edwards, C. S. Taylor, A. S. Russell

Solubilities and densities are reported for alumina hydrates in NaOH solutions under the conditions of the Bayer process employed to purify alumina for aluminum production. The equilibrium constants for reactions to form A102- accurately correlate the effects of NaOH concentration on the solubilities; the temperature coefficients of the equilibria lead to heats of solution of 7.34, 4.76, and 5.24 kcal for the a trihydrate, a monohydrate, and ß trihydrate, respectively. Moderate calcination does not change the solubility of the a trihydrate but increases that of the a monohydrate. At solution temperatures above 100°C, the trihydrates transform rapidly to a monohydrate. Hydro-thermally produced a monohydrate is the stable phase above 20°C. CORNERSTONE of the aluminum industry, the Bayer process for alumina production is based on the difference in solubility of hydrated alumina in NaOH solutions between 170" and 40°C. Solubilities and densities in this system were determined thirty years ago by M. Tosterudl under the direction of J. D. Edwards and C. S. Taylor. The solubility data, which still appear more concordant than those in the literature, are employed to sort out the complex equilibria in this system. The nomenclature for the alumina hydrates is that presented in The Aluminum Industry' and more recently summarized in Alumina Properties.3 a trihydrate is the purified phase analogous to gibbsite, a monohydrate is similarly akin to boehmite, and ß trihydrate is sometimes known as bayerite. Literature Goudriaan4 reviewed the early literature on alumina in NaOH solutions and presented data on the solubility at 30°C of several forms. The gel precipitated from aluminum sulphate or chloride with ammonia and dried at 130" to 140°C had the highest solubility but was unstable, its solubility being cut to one-tenth on standing in NaOH. The solubility of the gel was decreased one-third on calcination at 300" to 400°C, while that of the gel transformed in NaOH at room temperature to a crystalline trihydrate was unchanged on calcination. The preparation produced by slow hydrolysis of sodium aluminate solution with CO, in the air gave solubilities in rough agreement with later values for a trihydrate. The solubility of this form was increased slightly by the calcination. Fricke and Jucaitis5 extended the work to 30" and 60°C with a trihydrate. They also gave solubilities for ß trihydrate (bayerite b), although the residue belonging to the left branch of the solubility curve corresponded to a trihydrate. The residues at high NaOH concentrations were mono and trisodium aluminates, the latter being 3Na2O . AL2O3 • 6H2O. Solubilities of a trihydrate at 95°C and of a monohydrate at 150" and 200 °C come from the work of Magarchak.6 a trihydrate transformed to a monohydrate above 95°C. A few measurements on the solubility at 25°C of an alumina trihydrate prepared by slow hydrolysis of NaAIO, solutions were presented by Sprauer and pearce.? Their analyses showed the monosodium aluminate to have the composition Na2O.Al2O3-2.5H2O.

Jan 1, 1956

Established as a Division December 15, 1948 Clayton G Ball, Chairman Louis C Raymond, Vice-Chairman Sheldon P Wimpfen, Vice-Chairman Henry T Mudd, Vice-Chairman A H Lindley, Jr, Secretary-Treasurer Division of Foreign Activities U S Bureau of Mines Washington, D C

Jan 1, 1956

By C. G. Albert

The clay particles of 2 microns or less required for modern paper coating are predominantly flat plates, lying smoothly on the sheet and producing a high gloss. Operating speeds of today's coating machines necessitate a clay composition of 60 and sometimes 70 pct solids as against the 35 to 40 pct required in the past. Since clays in suspension may solidify in flow, only those of intrinsically low viscosity can be used as high coating solids. THE literature of paper technology contains a number of articles having reference to developments in the field of coating and filler clays for use in paper manufacture. Much of this information has not been included in mining publications and has therefore not been readily available to all in the mineral industry. Recent developments in this field, including spray drying of clays, are presented here. U. S. Bureau of Mines figures for 1952 indicate that the paper industry consumes more than 50 pct of all kaolin produced and sold in the U. S. As most of the kaolin used by the industry comes from Georgia producers, the fraction of their output destined for paper use is thus appreciably higher than 50 pct. Small wonder that the kaolin industry, especially in Georgia, is highly sensitive to the quality requirements of paper mills and must respond promptly to technological developments in paper manufacturing. The paper industry itself is not the ultimate consumer. For the greater portion of the clay the end product is the printed page, and the demands of printing and publishing have sparked some of the technological advances in paper making which have, in turn, brought about methods employed in the kaolin industry. As compared with the product of 20 or 25 years ago, one of the most striking characteristics of the graphic arts today is the mass production of quality printing of fine pictorial work, much of it in full color. During this time periodicals with printing standards close to those of yesterday's slick-paper publications that were printed on a slow schedule and for a limited circulation have grown to the point where they go out to many millions of readers, often at weekly intervals. The complexity of technological improvements brought about by this increased circulation is probably not appreciated even by technical people, unless they have had reasonably close contact with the industry. The advance has come about through developments not only in the art of printing, but also in the field of paper making and even at the level of clay mining and processing. The smoothness required for faithful reproduction of the kind of printed matter under consideration is attained with a clay-coated paper. Since the distribution expense of the publication will depend to a great extent on its weight, the paper used must not be too heavy. This means a lower basis weight than was normal for conventional clay-coated papers some 25 years ago. And for this mass production market it becomes necessary to provide a paper having these and all the other required characteristics at a very moderate price—not the premium price conventional clay-coated papers formerly demanded. This challenge has been met by a new method of producing coated paper. In the past, application of clay coating to paper was a conversion operation, performed separately from the making of the base sheet. The newer development is called machine coating. Here application of the coating is an integral step in a continuous process by which wood pulp, clay, and other ingredients are manufactured into a sheet of coated paper. Many more problems are involved in this procedural change than are apparent at a casual glance. The coating operation, for example, must function at much higher linear speed than could be obtained with coating mechanisms previously employed. The application machinery developed to meet this requirement necessitated changes in composition of the coating color.* This created new requirements, summarized below, for the clay employed as coating pigment. In addition to smoothness, a relatively glossy printing surface is needed, and to a large measure it is the function of the coating clay to make possible the development of both these surface characteristics. Traditionally, pigments such as satin-white, prepared by reacting lime with paper-makers' alum, were used to assist in producing a high finish. However, economic considerations and others preclude large-scale use of such material in the new processes. In the 1930's Maloney' discovered that a certain particle size fraction of kaolin, consisting

Jan 1, 1956