Search Documents

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

Arrangements have been completed in New York whereby the re- sources of The Engineering Foundation, under the auspices of the four principal national engineering societies, are placed at the disposal of the National Research Council, which was appointed by the National Academy of Sciences* at the request of President Wilson. The object of the Council is to coordinate the scientific research work of the country in order to secure efficiency in the solution of the problems of war and peace. The Council was without funds until The Engineering Foundation, established to further scientific and engineering research, offered to place its resources at the Council's disposal, including the services of its secretary, Dr. Cary T. Hutchinson, to act as-secretary of the Council. The offer was accepted and plans for immediate activities have been placed in the hands of an executive committee. In indicating how thoroughly, every branch bf science and engineering is represented, Dr. George E. Hale, Director of the Mt. Wilson Solar Observatory, and Chairman of the Council, when he was in New York attending to the details of the arrangement, called attention to the personnel of the body, saying that it is the purpose to enlist the cooperation, in the solution of our industrial and military problems of a scientific character, of every possible established agency. Medicine, for example, is represented on the Council by Dr. William H. Welch, President of the National Academy of Sciences, Brigadier General William C. Gorgas, , Surgeon Crenera.1 of the United States Army, Dr. Simon Flexner, Director of the Rockefeller Medical Institute, and Dr. Victor C. Vaughan, Past President of the American Medical Society; biological science by Dr. Edwin G. Conklin, Professor of Zoology, Princeton University; chemistry by Dr. A. A. Noyes of Massachusetts Institute of Technology and Dr. L. H. Baekeland; physics by Dr. A. A. Michelson of the University of Chicago; and electricity by Professor M. I. Pupin, of Columbia University.

Jan 10, 1916

By James F. Kemp

In submitting an additional contribution to the discussion on ore-deposits in the recent volumes of the Transactions, it is my desire to adhere closely to matters of material importance as affecting the actual processes. Judging from the discussion by Professor Van Hise, and from one or two reviews or other articles by associates of his in geological work, the impression seems to prevail that, in so far as my paper* referred to his masterly essay, I was guilty of misconceptions regarding both the part attributed by him in it to the igneous rocks and the ubiquitous presence of the ground-water. I should regret extremely to be wanting in these particulars or to have misunderstood one for whose great services in this and other branches of geology no one has a higher esteem than myself. I have, however, in the most careful way, and with these points in mind, read his essay again, and, taking it as a whole, I cannot gain any different impression of relative magnitudes than the one first received. The importance of the igneous phenomena and the restrictive influence of the processes described by " cementation " in their effect upon the ground-water, as set forth in Professor Van Hise's "Discussion" (Trans., xxxi., 292), impress me as being in very marked contrast with the same things in his first essay. If the point seems to anyone of sufficient importance, it can easily be decided by reading the originals. My paper was the result of some years of observation, reading and reflection, and was meant to be an independent contribution, controversial only in some subordinate particulars. In depicting the drama of the deposition of ores, I cannot but feel that Professor Van Hise assigned to the chorus and the scene-shifters some characters which, it seems to me, should

Jan 1, 1903

By J. P. Sheehan, W. R. Hibbard, M. Baeyertz

This paper deals with molybdenum modifications of 5140 steel that have the same hardenability but a better tolerance for phosphorus than the AISI-SAE 5140 grade. Lack of toughness in steels with higher than normal phosphorus contents is well known to metallurgists. This problem is troublesome even within normal phosphorus ranges, if the heat treatment or the design of the part or the service is critical. Under such unfavorable conditions and also in the case of phosphorus contents toward the upper side of the commercial range, the use of molybdenum to replace a part of the chromium in 5140 steel provides a factor of safety. The toughness of steel is variously exhibited in different mechanical tests; broadly the term is applied to the capacity of the steel to deform prior to fracture. Defined in this way, toughness is considered to be an inherent quality that depends upon the composition and structure of the steel, and also upon its temperature during deformation and fracture in the test. In the present state of our knowledge, the type of mechanical test needs to be included in any discussion of toughness, because the revelation of this quality in steel depends on the stress state and rate of stressing imposed by the test. In comparing the toughness of one steel with another by laboratory testing, it has long been customary to use notched tests that impose severe constmint to deformation, and then to test over a range of temperatures to obtain the so-called transition. At temperatures above the transition, the steel fails after considerable deformation and absorption of energy. Below the transition, less energy is absorbed as the steel fails largely by cleavage. The transition range itself is characterized by a more or less abrupt change in energy absorption and type of fracture. The conventional V-notch Charpy impact test has been used exclusively in the work covered by this report. For the steels under study, rather sharp transitions are obtained with this test, at testing temperatures that are easily obtained in the laboratory. The position of the transition on the testing temperature scale provides a rather sensitive index of the toughness of the steel, when the steels under study are similar in character as they are in this work. Turning to the metallurgical reasons for the greater toughness of one steel as compared to another, the authors propose to limit the discussion to the small field under study. Only one structural state is considered, tempered martensite of a hardness of about 28 Rockwell C or 269 Brinell. The study deals first with the loss of toughness in AISI-SAE 5140 steel caused by increasing the phosphorus content from about 0.020 to 0.040 pct. A second part of the work deals with counteracting this loss in toughness by replacing a part of the chromium by molybdenum. A series of molybdenum modifications was studied, in each of which the chromium was reduced sufficiently to duplicate the hardenability of 5140 steel. Phosphorus affects the toughness of steel in two ways. An inherent lack of toughness of phosphorus-bearing ferrite as compared to low phosphorus ferrite has often been noted. Jolivet and Vidall have shown that phosphorus has the same effect in tempered martensite in chromium steels. The other well known effect of phosphorus is to make steel susceptible to temper embrittlement. Temper brittleness is a loss in toughness brought about by tempering steel within a limited temperature interval somewhat below the A1 temperature. In most of the standard AISI-SAE alloy steels, this temperature interval is approximately 850-1100°F. Either of these types of loss in toughness is easily followed by the shift in the transition temperature obtained with the notched-bar impact test. The data to be presented show the beneficial effect of substituting molybdenum for a part of the chromium in 5140 steel with either moderate (0.020 pct) or high (0.040 pct) phosphorus contents. Both the inherent lack of toughness of phosphorus-bearing steel and temper brittleness are counteracted by this use of molybdenum. The work of Jolivet and Vidal mentioned above shows the detrimental effect of phosphorus on the toughness of tempered martensite in the absence of temper embrittlement, as well as the temper brittleness caused by phosphorus. They used two steels, essentially 0.25 pct C-1.4 pct Cr, with 0.044 and 0.013 pct P, respectively. The nonembrittled state was obtained by quenching in oil from 1610°F, then tempering for one hour at 1200°F and quenching in water. In this state the transition temperature range of the low phosphorus steel in the notched-bar impact test was below that of the steel with 0.044 pct P. An additional treatment of 24 hr at 975°F (that is, in the embrittling range) caused both steels to lose toughness, but the high phosphorus steel showed the greater embrittlement. Recently Hollomon2 has published a comprehensive survey and bibliography of the literature on temper brittleness, to which the reader is re-

Jan 1, 1950

By John Campbell

An approximate theoretical model is proposed to quantitatively predict freezing ranges Tf and hydrostatic tensions P developed within solidifying binary alloys, allowing for a certain amount of diffusion of solute in the solid during solidification. The maxima in ATf and AP as functions of composition are shorn to occur at smaller solute concentrations than would be expected from the equilibrium diagram, and are found to correspond closely to experimentally observed maxima in microporosity. THE freezing range of simple binary alloys appears to have been little studied, except for certain indirect observations on the defects, particularly microporosity and hot tearing, arising in long freezing range materials. Two theories relating to the freezing range of alloys and its effect upon porosity are reasonably well established, and appear to have been held in isolation from each other: a) From purely equilibrium considerations early researchers expected that an increase in solute content of an alloy should increase the freezing range (defined here as the equilibrium freezing range ?Tf = Tl-Ts where TL and Ts are the liquidus and solidus temperatures, respectively) and thereby increase the width of the pasty zone for a given set of conditions. This in turn should increase the difficulty of feeding the residual liquid through the dendrite mesh to compensate for the contraction on solidification, and consequently tend to increase the observed amount of porosity. From qualitative observations on steels Czikel1 reports an increase in porosity with increasing carbon content up to 0.46 pct C. More careful measurements by Whittenberger and Rhines2 on fourteen different alloy systems showed an approximately linear relation between ?Tf and pct porosity (although unfortunately the precise experimental data is not given). b) Conversely however, other authors3"5 propose that porosity is reduced by the presence of increased amounts of eutectic present at the final solidification temperature. Lees7 and Bochvar6 claim that the hot tearing of alloys is similarly reduced. Scheuer8 has put forward a theory to explain this effect, Fig. 1. The argument is basically that solidification progresses on a plane front through a relatively open dendrite network and is thus (the argument is not developed more explicitly) easier to feed. One would expect effect a) to operate at low solute contents, and b) to be important at higher solute contents, so that at some critical composition a max-

Jan 1, 1970

By J. C. Branner

DuriKg the past two or three years I have seen statements regarding the first discovery of fullers' earth in this country that seem to require correction or modification. One appears again in the Mineral Resources of the United States for 1909, part II., p. 738, where it is said that 'fullers' earth was firat discovered in the United States at Quincy, Fla., in 1893." In this connection the following bit of unpublished history concerning fullers' earth in the State of Arkansas is worthy of attention. In April, 1891, when I was State Geologist of Arkansas, a Swede named John Olsen, formerly a copper-miner in Michigan, but then living south of Little Rock, brought me a sample of what he thought mas fullers' earth. He reported that it was from near the town of Alexander, the locality being 1 S. 13 W., section 8, SW. quarter of the SE. quarter. My chemist, Dr. R. N. Brackett, analyzed the material, and reported: Per Cent. Silica,.....SiO2 .... 63.19 Alumina,.... A12O3 .... 18.76 Iron,.....Fe2O3 .... 7.05 Lime,.,...CaO .... 0.78 Magnesia,.... MgO .... 1.68 Potash,.... K2O ,... 0.21 Soda,.....Na2O .... 1.50 Loss on ignition,........7.57 100.74 Water at 110° to 115° C. = 7.84. Another sample from about the same locality, also brought by John Olsen, on analysis by Dr. Brackett gave :

Jan 1, 1913

By M. Garfinkle, W. D. Klopp, W. R. Witzke

The tensile properties of binary W-Re alloys containing up to 33 at. pct Re were determined at temperatures from 78" to 3630°F. Elongations as high as 260 pct were observed in electron-beam-melted tungsten containing 23 at. pct Re when tensile-tested at 3630°F after a 1-hr anneal at 3090°F. All alloys tested under these conditions with rhenium contents between 20 and 28 at. pct exhibited elongations of at least 200 pct. These alloys also showed enhanced grain growth rates. The values of strain-rate sensitivity ranged between 0.2 and 0.3 for the alloys exhibiting high elongations. Houlezler, for swaged alloys tested just above the re-crystallization temperature, strain-rate sensitivities as high as 0.8 were observed. The high-temperature strengths of the high-rhenium-content alloys were also less than those of alloys with intermediate rhenium contents. ALLOYING with rhenium has two distinct effects on the mechanical properties of tungsten. One effect occurs in dilute solid solutions and is most clearly seen in the lowering of the hardness and of the ductile-brittle transition temperature at about 5 at. pct Re.1-3 The second effect occurs in the concentrated solid solution at about 25 at. pct Re, and is characterized by twinning and a larger decrease in the ductile-brittle transition temperature. An aspect of the high-rhenium-content alloy which has received little attention is the higher-than-usual tensile ductility at 3500°F.3 Anomalous high ductility has been observed in several other alloy systems. usually associated with a phase transformation or a solid-solubility limit.4'5 The phenomenon is now commonly termed superplasticity. High-strain-rate sensitivities6 and grain boundary sliding7 have been reported for materials that undergo superplastic deformation. Also, it has been found that superplastic materials usually have a very fine grain structure (less than 10 pm).8 and it has been proposedg that such a structure alone is sufficient for superplasticity. The purpose of the present study was to further characterize the high-temperature tensile properties of W-Re alloys to determine the conditions under which they might be superplastic. Tensile and selected strain-rate sensitivity tests were conducted on alloys containing 0 to 33.3 at. pct Re at temperatures from 78" to 3630°F. Grain-growth rates were also determined on most alloys at 3630°F. Fig. 1 indicates the compositions evaluated and their locations relative to the solvus line in the tungsten-rich end of the W-Re phase diagram. Twelve binary W-Re alloys containing up to 33.3 at pct Re were double electron-beam-melted and subsequently fabricated to 0.3-in. rod by extrusion and swaging. The starting materials were commercial powders of tungsten and rhenium with impurity levels as listed in Table I. The various blended W-Re compositions were hydrostatically pressed at 70 ksi. The pressed bars were drip-melted into 1.5-in.-diam ingots and then remelted into 2-in.-diam ingots at a chamber pressure of 10~5 torr. The ingots were canned in molybdenum and extruded to round bar at a reduction ratio of 6:l. The alloy extrusions were swaged to about an 80 pct reduction at 2100" to 2900°F. Buttonhead tensile specimens with a reduced section diameter of 0.16 in. and a gage length of 1.0 in. were centerless-ground from the swaged bars

Jan 1, 1970

Executive Committee, Board of Directors C E Reistle, Jr, Chairman, H DeWitt Smith, Vice-Chairman, T B Counselman, Grover Holt, A W Thornton Finance Committee, Board of Directors Andrew Fletcher, Chairman, R B Caples, C R Dodson Investments Erle V Daveler, '57, Chairman, Henry Krumb, '59, John E Warren, '57, G F Moulton, ex officio as Treasurer, Andrew Fletcher, ex officio as Chairman, Fi¬nance Committee Endowment W W Mein, Jr, Chairman, N G Alford, E V Daveler, W J Coulter, J V N Dorr, R B Gilmore, J B Haffner, 0 H Johnson, Henry Krumb, D H McLaughlin, J R McMillan, J B Morrow, L F Reinartz, Wilfred Sykes, C E Weed Honorary Memberships Andrew Fletcher, Chairman, L F Reinartz and H DeWitt Smith, ex officio as Past Presidents, C E Reistle, Jr , ex officio as President, M L Rai¬der, '60, Henry Krumb, '58, D H McLaughlin, '57, P D Merica, '59

Jan 1, 1956

On Friday, Jan. 17, the thirteenth impression of the Perkin Medal was presented to Dr. Frederick Gardner Cottrell, at a meeting of the New York Section of the Society of Chemical Industry, held at the Chemists' Club, in New York City. The presentation address was delivered by Dr. C. F. Chandler, Senior Past President of the Society. The medal was awarded for the recipient's work in the electrical precipitation of suspended particles in gases. Dr. Cottrell's career, which is so familiar to members of the Institute, was sketched by Dr. Chandler. He told at some length of the experiments leading up to the final solution of electrostatic precipitation, which has done so much to solve the problem of smelter smoke. The principal interest in Dr. Cottrell's speech of acceptance lay in his remarks about helium, the production of which has been so reduced in cost that it has practically supplanted the use of hydrogen for inflation purposes in war balloons. He said: "Two or three weeks after war was declared in 1917, Dr. R. B. Moore attended a meeting of the American Chemical Society in Kansas City. At the general session, Mr. Seibel of the University of Kansas, gave a paper on krypton and xenon in some of the natural gases of Kansas. At the end of his paper, he expressed regret that at such a time, when everyone was thinking of war problems, his paper was of a purely scientific nature and had no practical bearing on the war. Dr. Moore immediately got up and said that he did not agree with Mr. Seibel. The presence of helium in those wells could, and should, have a very practical bearing on the war, as this gas could be extracted in quantity from the natural gas and used for balloons and Zeppelins. He pointed out some of the natural advantages of helium over hydrogen, and quoted Sir William Ramsey's letter advocating the use of helium for airships. The general attitude of those present was one of scepticism, so he finally asked Dr. Cady for his opinion who stated that he believed-the thing could be done, but was very doubtful whether it could ever be made practical on account of the cost." Dr. Moore in a letter wrote: "That same day I talked to Dr. Parsons, who was present at the meeting and was returning to Washington almost immediately. I told him what had happened, and that I believed the matter should be taken up by the Bureau at once and presented to the War Department. He promised to do this as soon as he got to Washington; and I know that he did take the matter up with other Bureau officials." Dr. Cottrell continued in part: News of Ramsey's suggestions also reached this .country through other channels and eventually came to our attention. Professors Satterly and Patterson of the University of Toronto commenced experimentation of the subject Jan. 1, 1916. Col. G. A. Burrell, who headed the research department of the Gas Warfare Service at the American University, tells me that Cady's experiments had also suggested similar possibilities to him.

Jan 3, 1919

By C. V. Millikan

Production engineering has continued its rapid progress during the past year. Many engineering efficiencies long practiced in other industries are being rapidly accepted by the oil industry, and every branch of development and production work is undergoing study that is reducing the time and hazard in the drilling of wells even for greater depths, is securing better service from equipment, and is obtaining greater ultimate recovery from the reservoirs. Deviation of Drill Holes Deviation of drill holes probably has attracted greater and wider study than any other subject. Until about one year ago it had been given little attention. Some California operators knew the common magnitude of deviation, but Mid-Continent operators hesitated to believe that holes could be drilled so crooked. The great emphasis and publicity given to the seriousness of the problem resulted in the design of many instruments to record the deviation by chart or photograph. Instruments which would give the direction as well as deviation were not generally favored because of the grave fears of the legal complications which might result if the bottom of a producing well should prove to be on a neighboring lease. With all the instruments available for determining deviation, the use of etching on a glass bottle by hydrofluoric acid is still the most common method employed. The beneficial result of this earnest effort to drill straighter holes is proved by a comparison of deviation of wells completed recently with those completed over a year ago. The time of this change is arbitrarily taken as Jan. 1, 1929, as at that time the operators were aware of the deviation which usually occurred, and most of them were making some effort to reduce it. Table I shows averages of wells completed by several companies. Data on a few wells outside the greater Seminole area are

Jan 1, 1930

Tile National Research Council announces further appointments to National Research Fellowships in physics and chemistry. The object of the National Research Council in maintaining a system of research fellowships is to promote fundamental research in physics and chemistry primarily in educational institutions in the United States. Fellowships are awarded to persons who have demonstrated a high order of ability in research for the purpose of enabling them to conduct investigations at educational institutions which make adequate provisions for research: in physics and chemistry. The new appointments are as follows: In Chemistry.-Warren C. Vosburgh, of New York City, B. S. Union College, 1914, A. M. Union College, 1916, Ph. D. Columbia University, 1919. Research assistant to the Professor of Chemistry at Columbia University for the past six months. George Scatchard, of New York City, A. B. Amherst College, 1913, Ph. D. Colt tibia University, 1917. Formerly research assistant to the Professor of Chemistry at Columbia University and instructor in organic chemistry: First Lieutenant. Sanitary Corns. U. S. A.

Jan 7, 1919

SECTION I PAGE PAGE Bulletins Wanted v Local Section News xv St. Louis Meeting v Affiliated Student Society Notes.. xviii National Engineering Societies in California's Mineral Resources National Service..: vii ? for War Purposes xix Members in Officers Reserve Corps xi Forthcoming Meetings xx Resolution by Military Engineering ? Library xxi Committee xi Membership. :: xxiv Personal :.. xii Biographical Notice of David H. Employment xiv Browne xliv Alaska Mining and Engineering Institute Committees xlvii Society xv Officers and Directors liv

Jan 6, 1917

By W. W. Gorr, R. Smith, E. H. Wyche

THE combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W? and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. DEVELOPMENT OF THE NEW STEEL For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield 18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators 'then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, o.58; Ni, 7.28; Cr, 17.6o; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1946

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By George C. Ference

Sulfur is the 13th most common element in the earth's crust, constituting approximately 0.05% of the total. It occurs naturally in its elemental form, as metallic sulfides, nonmetallic sulfates, and as combined or free sulfur in natural gas, crude oil, and coal. COMMERCIAL SOURCES Most of the sulfur that is consumed is converted into sulfuric acid before use; therefore, it is not necessary to recover sulfur solely in its elemental form. Processes for recovery are peculiar- to the types of reserves being processed. The major commercial processes as well as the general geographic locations where the appropriate reserves occur are listed in the following. It should be noted that the sulfur values may be recovered as the primary product, as a coproduct with other materials, or as a byproduct. Elemental Sulfur 1) Frasch mining is used for subterranean deposits of elemental sulfur around the Gulf Coast areas of the United States and Mexico. Generally, but not exclusively, such deposits are located in salt dome structure. 2) Autoclaving, flotation, or solvent extraction of surface deposits of elemental sulfur is practiced throughout the world. 3) Extraction and conversion of hydrogen sulfide from sour natural gas into elemental sulfur is done principally in Canada, France, and the United States. 4) Conversion of metallic sulfides from pyrites into elemental sulfur is done via the Outokumpu process in Finland. 5) Catalytic cracking and hydrocracking of sulfur-bearing crude oils to produce elemental sulfur is done worldwide. Desulfurization of refined petroleum products also yields elemental sulfur. 6) Recovery of elemental sulfur from sulfur-bearing oil sands (Athabasca tar sands) has been initiated in Canada. 7) As of this writing (1970), a plant has been constructed for the thermal decomposition of gypsum to produce elemental sulfur in the United States. Sulfuric Acid Sulfur values in the form of sulfuric acid are recovered via: 1) Recovery from smelter gases throughout the world. 2) Roasting of pyrites throughout the world with iron sinters as a byproduct. 3) Roasting of anhydrite with cement as a coproduct, primarily in Europe. 4) Processes currently are being developed for recovery of sulfuric acid from combustion gases resulting from the burning of high-sulfur-content fuel. Other Sulfur values also are recovered from waste products which normally occur in highly industrialized areas. Some examples are: coke-oven gases, sludge sulfuric acid, and pickling liquors (ferrous sulfate).

Jan 1, 1976

CONTENTS PAGE East Texas, except the Gulf Coast-H. Vance 3 Gulf Coast-L. P. Teas 8 Texas Panhandle-C. C. Rae 16 North Central Texas-H. F. Smiley 23 North Louisiana, South Arkansas and Mississippi-B. C. Craft 25 Oklahoma-C. H. Pishny, Raymond M. Carr and E. J. Dickinson 31 Kansas-E. A. Koester 35 Rocky Mountain District-C. D. Johnson 46 Illinois and Indiana-T. Wasson 49 Michigan-T. Wasson 52 Eastern States-P. D. Torrey and W. H. Young, Jr 58 West Texas and New Mexico-W. V. Vietti. Published as a Supplement.

Jan 1, 1933

By Paul H. Hunt

MANY MISUNDERSTANDINGS have arisen regarding -Al the purchase by the Government of 24,000,000 oz. of domestically produced silver annually for the next four years at a price of 64 1/2c. to the producer. Some editorials have an¬nounced rather sarcastically that be¬cause of the strong western silver bloc in Congress, the Administration is paying a bonus of approximately $22,000,000 to a few large silver produc¬ers of the West, the amount being figured on the total purchase of about 100,000,000 oz. and the difference between the Government price and the world price for silver. Actually the Government will make a profit on this purchase, due to seigniorage, of something over $60,000,000. The 96,000,000 oz. of silver, for which the producers will receive approximately $62,000,000, will be produced in association with at least $100,000,000 worth of lead, zinc, copper and gold; the greater part of this $162,000,000 worth of metal will be produced at little profit to the mining companies, as will be shown later, because of the low prices for lead, copper and zinc. This amount of money will be spent largely for labor and supplies, thus greatly relieving the national burden of unemployment. Certainly, western mining, in the purchase of this silver, is not victimizing the Federal Government.

Jan 1, 1934

By David J. Dunn, Richard G. Martin

Of many physical parameters critical to design of grinding processes, impact of grinding media is among the most difficult to measure or predict. Yet impact of falling grinding balls, pebbles, or rods accomplishes the fine grinding essential to metallurgical recovery of most important minerals. Unfortunately, the same impacts that break ore fragments deform or crack grinding mill liners. A project was undertaken at Climax Molybdenum Company to measure impact forces in operating ball mills so that they might be used to calculate stresses in liner materials and be correlated with service performance of mill liner alloys. Towards that end, a method of measuring impact forces on ball mill liners using an instrumented grinding ball has been developed. Preliminary tests show that impact forces and contact stresses imposed on bare mill liners are quite high but are greatly reduced by cushioning when coarse ore particles are crushed between balls and liners.

Jan 4, 1978

By W. J. Carlson, I. lwasaki

Manganese and silica in nonmagnetic tailings from the direct reduction-magnetic separation step were so closely associated that no physical concentration methods were effective. Dilute sulfuric acid dissolved manganese and iron rapidly; manganese in the form of silicates was virtually insoluble in sulfuric acid solutions, thereby governing the maximum extraction attained by leaching. Autoclave leaching at elevated temperatures and at high oxygen pressures reduced the iron extraction to less than one tenth without affecting the manganese extraction. There was an indication that autoclaving solubilized the manganese silicates appreciably. Elimination of iron from leach solutions was carried out by aerating the solution in the pH range of 6.5-7; a platinum-calomel electrode pair provided a reliable indicator for the end point of iron removal. The purified leach solutions were free of interfering impurities for the recovery of manganese as metal, dioxide, or carbonate. Manganiferous iron ores of the Cuyuna Range, Minn., are too low in iron content to be directly useful as iron ores, and too low in manganese content to be termed manganese ores. Common methods of physical beneficiation such as gravity concentration and flotation have not been successful in upgrading this material. The R-N process, when applied to manganiferous iron ores,1'2 produces sponge iron by direct reduction of iron oxides, while leaving manganese as manganous oxide. From fine grinding and magnetic separation of the reduced ore, a tailing is produced which is relatively rich in manganese and low in iron content. The nonmagnetic tailing can readily be leached with acids and then further processed to recover manganese in various forms. In this way, two processes, neither of which would be an economic solution to the Cuyuna ore problem by itself, may be combined to produce two marketable products, thereby rendering the over-all process economically more attractive. This article reports on the results of a leaching study on the nonmagnetic tailings, both in a batch agitation vessel and in an autoclave; on the problems involved in the purification of leach liquors by aeration; and on the recovery techniques used to produce manganese metal by electrolysis, manganese dioxide either by electrolysis or by autoclaving, and

Jan 1, 1968

By T. Vasilos, J. T. Smith

THE mechanism of pressure sintering, or hot pressing, for ceramic materials, has been investigated by several researchers.1-8 Plastic flow has been suggested as the rate-determining mech-anism1,2 while grain boundary sliding3,4 and fragmentation processess have been found controlling in other studies. Vasilos and Spriggs5,6 have reported that pressure sintering occurs by a diffusion-controlled mechanism. For the pressure sintering of metals, investigations with lead7 and with tin6 have not identified the operative mechanism during consolidation of these powders. This note reports the results of a pressure sintering study initiated to determine the mechanism controlling the densification of spherical copper powder. Temperatures of 300°, 400°, 500°, and 600°C at 2500, 5000, 7500, and 10,000 psi pressures were investigated. The copper powder for this study was obtained from Metals Disintegrating Co., Elizabeth, N.J. The minimum purity was reported to be 99.9 pct. The powder size was -325 mesh and a lineal analysis showed the average size to be less than 1 p. An alumina die body and punches were employed. Graphite spacers were placed between the copper powder and the punches before pressing. It was expected that the graphite would form carbon monoxide with any entrapped air and form a reducing atmosphere within the die cavity. This condition was generally realized during pressing although a minor amount of oxidation occurred at 500" and 600°C. The oxide particles were located randomly in the pressed samples and were not considered to influence the densification process. Calibration tests showed the temperature of the copper pellet to be about 20°C less than the die wall temperature, probably resulting from heat losses through the punches. This difference was compensated during the experimental pressing operations. The hot pressing equipment employed for this work has been described by Spriggs et a1.9 and was calibrated with a Baldwin-Lima-Hamilton load cell. Travel of the punches was monitored with a dial indicator showing increments of travel to 0.0005 in. Relative density was calculated at selected time intervals for a known copper weight, punch travel, and die diameter. The accuracy of this calculation was *1 pct. Average grain size after hot pressing was obtained by lineal analysis. Typical densification curves are presented in Fig. 1 and Fig. 2 where relative density is plotted vs log time as a function of applied pressure for the 300" and 600°C pressure sintering temperatures, respectively. The curves for 400" and 500°C were similar to those at 300°C and consequently are not shown. The curves at 300°C as well as 400" and 500°C do not show an end-point or limiting density for a particular applied pressure. At 600°C, a density in excess of 95 pct of theoretical has been reached such that further densification is extremely slow for the 5000, 7500, and 10,000 psi pressures. It is suggested that further densification at these pressure levels may be retarded or prevented by discontinuous grain growth, by entrapped gases, and by other microstructural limitations as described by Cob1e.10 The curve for 2500 psi hot pressing pressure is a straight line over the time interval although a slight change in slope may be occurring at the last time intervals. The plastic flow models,1,2 derived for hot pressing, predict the existence of an end-point (or limiting) density dependent on the yield point of the material at the temperature of interest. The yield stress of copper at a 0.005 strain level has been

Jan 1, 1965