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By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.' Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

By R. C. Amero

FULLERS earth is a general name applied to claylike minerals that have high natural ad-sorptive powers. They are usually distinguished from ordinary clays by a higher content of combined moisture and a lower apparent density. The definition is based on the ancient use of the material for fulling, or cleansing woolen cloth of oil and grease; a more modern definition should mention the ability to decolorize oil and should differentiate between fullers earth, which is naturally active, and certain bentonites which only develop decolorizing power after being leached with strong mineral acids. The distinction between fullers earth and activable bentonite is not a sharp one, since all types of intermediate clays can be found that are more or less naturally active, yet more or less responsive to acid treatment. The differences seem to depend somewhat on the amount of leaching that has been effected by natural ground waters. Physical Properties The principal mineral constituent of activable bentonite is montmorillonite, a hydrous aluminum silicate to which the following formula is generally assigned: Al,Si,O,, (OH), • 12H,O Fullers earth, as well as bentonite, is usually composed of some variety of montmorillonite, but in the United States the largest tonnage of fullers earth is mined from deposits of attapulgite. Attapul- gite is a clay mineral composed of monoclinic crystals of colloidal size, having a fibrous shape similar to that of asbestos. A sectional model of the attapulgite "molecule" is shown in Fig. 1. A single unit is about 18.0 A wide and 12.9 A high. The length of the molecule is variable, but this same molecular pattern is repeated to form needlework crystals, rather than flakes, as is characteristic of the montmorillonite crystals. Attapulgite has been assigned the following formula,' although actually, the magnesia has been largely replaced by alumina: (0%) . (OH), • Mg, . Si, • Olp . 4H20. The fibrous nature of the mineral is clearly shown in the electron micrograph, Fig. 2. Although the deposits contain 5 to 30 pct quartz and carbonate minerals, impurities in the commercial products are held at a low level, principally by selective mining on the basis of oil decolorizing efficiency. The particle size distribution of this fullers earth has been estimated from settling rates, using sodium citrate as a dispersing agent.' Since Stokes' law only applies to spherical particles, the equivalent particle diameter calculated below is probably more nearly an index of diameter rather than length of the needlelike crystals: Eqnivalent Arbitrary Particle Distribution, Size Diameter Pci Classil3catian 0.05 mm 0.80 0.80 pct sand 0.05-0.02 mm 10.96 0.02-0.01 mm 9.65 42.10 pct silt 0.01-0.005 mm 11.40 0.005-0.002 mm 10.09 2-0.5 micron 10.61 0.5-0.2 micron 29.09 56.58 pct clay 0.2-0.05 micron 14.86 0.05 micron 1.96 The differential thermal analysis shown in Fig. 3 is unique and supports the theory that this is a distinct mineral species.' ~ Other general properties of the mineral as shown in Table I.

Jan 1, 1952

By Sherwin F. Kelly

Twenty five years of exploration has shown that the "geophysical dollar" is worth $1780 in the Orange Free State, $1488 on the Witwatersrand, $85 in Sweden, $28,000 in the Transvaal and $3500 or more in the U.S.

Jan 6, 1951

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By G. Sherburne Rogers

Introduction. ONE of the features of oil-field work that puzzles operator, chemist and geologist alike, is variation in the gravity of the petroleum produced, on neighboring leases or even from adjoining wells. Few fields in the United States yield oil that is of uniform gravity throughout; in some, fields the different grades are produced from different sands, in a few from different formations, and in many from different areas in the same sand. In a few cases, perhaps, a common assumption-that the heavier oil is derived from the lighter through the escape of the more volatile constituents-is valid, but many cases can not be explained in this way. Although in the California fields the specific gravity of the oil generally decreases with depth, there are numerous exceptions to this rule; and, as in many other regions the light oil is found nearest the surface, it is evident that evaporation underground is generally an unimportant factor. It is generally recognized that the great differences between petroleum from widely separated fields are due largely to differences in age and degree of metamorphism and to variation in the composition of the original organic matter; but in the writer's opinion some of these broader differences, as well as most of the minor variations in the character of the oil from any one field, are clue to the local action of natural reagents such as sulphur or oxygen. This is particularly likely to be true if the oil has migrated from one formation to another, as in the California fields; and in some areas it appears that variation in sulphur content may even afford a rough index of the extent or distance of the migration. It is the purpose of this paper to call attention to the chemical action of sulphur and oxygen on petroleum, to show that the gravity of the oil from any one field is intimately related to its sulphur content, and to discuss the possi-

Jan 7, 1917

By G.A. Moore, C. E. Sims

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By Clarence E. Sims, George A. Moore

INTRODUCTION IN previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficient time is allowed. For precise work, the method claims preference because the equipment for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the transformation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approximately 2 hr. While it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual error may be more or less constant between samples. For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temperature process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and evolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1948

By C. E. Sims, G. A. Moore

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

By C. D. Rugen

GROUND raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grindability characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. CHARACTER OF GROUND RAW MIX (KILN FEED) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size, whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since finer particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely fine kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1945

By Michael B. Bever, Carl F. Floe

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By H. V. Winchell

It seems to me that uniformity of mining law in North America must of necessity start with uniformity in each country. I understand that the Provinces of Canada have the right to make their own individual laws and conditions, to prescribe the terms under which the prospector or the applicant for mineral titles may secure the same. That is not true of the states in the United States. In this country, the Federal Mining Law was made applicable to the public domain, which, at the time of the adoption of this Act in 1872, was chiefly west of the Missouri River; it is impossible to locate a mining claim in most of our eastern states. It is true, however, that there are certain holdover rights, mostly obsolete, arising from the fact that at the time of the formation of the Confederation of States, the land that belonged to each state became the property of the Federal Government. I am not quite correc-t in that, it was sometime after the adoption of our Constitution, I think it was 1778, but those rights were largely, by agreement, surrendered to the Federal Government; but it is a fact that the great acquisitions of territory in the West, with the single exception of Texas, were of domain that came into the possession of the Federal Government and our Federal Mining Law applies to that territory. No state has the right to (by legislative enactment) enlarge upon the rights given by the Federal Mining Law, governing the acquisition of mining claims in its territory, within its boundaries. Each state, however, may, and some of them do, limit somewhat the rights given to the prospector. For instance, the Federal Mining Law provides that a claim may be taken, staked upon the public domain, of 600 ft. in width and 1500 ft. in length. Some of the states, like South Dakota and Colorado, have at times said "that is an excessive amount of land for a single mining claim; we will therefore limit it to 300 ft. or 200 ft. in width." There is, therefore, not any direct and immediate need for uniformity of mining laws in the United States, such as there might possibly be if it were considered at all desirable upon the whole in Canada. The initiation of mining rights under the Federal Mining Act is the act of discovery of valuable mineral in place, referring now to the lode mining claims, but the same is true of the placer claim. It is true that the emphasis has never been laid upon the word valuable and that

Jan 1, 1920

By T. S. Fuller

VARIOUS phases of the embrittlement of solid copper containing oxygen by the action of reducing gases at high temperatures through the work of many experimenters are familiar to readers of metallurgical literature. In 1900, Heyn1 recorded observations of copper being heated in hydrogen with the development of fine cracks, the result of the formation of steam within the metal through the action of hydrogen on the copper oxide usually found in copper. Archbutt,2 in 1905, published the results of experiments, showing that all oxygen can be removed from copper by heating to redness, for several hours, in hydrogen. Intercrystalline cracks and extreme brittleness developed. Archbutt attributed the brittleness to the reduction of oxides present in the copper. Bengough and Hill,3 in 1910, encountered the now well-known embrittlement at the outset of their investigation and stated in their paper: It soon became evident that the effect of any heat treatment depended largely on the presence or absence of reducing gases in the atmosphere of the furnace, as well as on its temperature. Hence it became necessary to adopt a somewhat elaborate scheme of heat treatment. The authors found embrittlement in separate experiments due to both hydrogen and carbon monoxide and concluded that: "The gases ruin the alloys after being heated to about 650° C. in their presence."

Jan 2, 1926

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably her product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too he, since finer particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely fine kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater dificulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1947

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably her product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too he, since finer particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely fine kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater dificulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1947

By J. Tarwater

The torsional testing of cylindrical medium-carbon steel specimens, heat treated to a high strength level, revealed a stress-strain relationship that was dependent on the direction of torsional plastic pre-strain. This Bauschinger effect was observed in prestrained specimens both with and without subsequent elevated-temperature strain aging. Yield stresses in strain-aged specimens exceeded those of simply prestrained specimens and the difference in stress was greater when the prestrain direction opposed the test direction. This behavior is discussed in terms of the classical dislocation pile-up using Cottrell's equation, A plastically prestrained strain-hardenable member, loaded in a direction opposite to the direction of prestrain, produces a stress-strain relationship differing appreciably from the curve representing reloading in the prestrain direction. This phenomenon, referred to as the Bauschinger effect, will be discussed in terms of the stress differences ob- served at a specified strain. The effect, dating back to the 1880's, was first attributed to grain boundary stresses. When later work revealed that the effect was also present in single crystals, revised theories attributed the diminished applied reverse stress to assistance from internal long-range stresses. These stresses have been associated with dislocation pile-ups or with dislocation arrays having analogous stress patterns. The stress patterns are subject to alteration by interaction with interstitial solute atoms and acceleration of the interaction may be accomplished with elevated-temperature strain aging. As discussed herein, the interaction showed a directional effect with regard to the applied stresses necessary for small plastic strains. Aside from the rigorous Bauschinger stress-strai relationship, which compares prestrained members, it is interesting to compare the stress-strain curve of a member being prestrained with that of a prestrained member being reverse loaded. For small strains which are a fraction of the prestrain deformation, the applied stresses of the reverse reloaded member are smaller. However, as the reverse strain approaches the prestrain value, the stresses approach equivalence. It has been reported1 that the stress required to return a prestrained specimen to its initial "zero" position generally exceeds the prestrain stress because of the work hardening occurring on potential slip systems during prestrain.

Jan 1, 1963

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, 'iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other *producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since her particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely he kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1948

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, 'iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other *producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since her particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely he kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1948

By IRVING H. WENTIVORTII

(New York Meeting, February, 1912.) THE little town of San Nicolás, Tamaulipas, Mexico, lies approximately 60 miles east of Linares, situated in the State of Nuevo Leon, and 150 miles SE. of Monterey, as shown in the sketch-map. Fig. 1. The place is reached from Monterey by the Tampico train as far as Linares, a distance of 92 miles, and then by coach the rest of the way. It is situated in a narrow valley between low hills, the houses forming one main street and a plaza. It is peopled by about 500 inhabitants. The climate is temperate, the thermometer ranging from 90° in summer to a few degrees below freezing-point in winter; but this severe weather only lasts a day or two at a time, when the " northers " blow. There are no streams in the vicinity, but water sufficient for the use of the people is obtained from wells. The rainfall is about the same as that in the rest of NE. Mexico. The rainy months are July, August, and September. The rest of the year is practically dry, with an occasional showery day or two during the winter, when a " norther " is blowing. Timber is abundant in many localities. There are two varieties of oak, besides mesquite, ebony, "maguira," "patol," and a number of other kinds of trees indigenous to this region. I. HISTORY. On the discovery of the silver-lead hearing veins occurring in this district, the mining-camp of San Nicolás was founded in 1767 by the Spaniards, and numerous mines were opened and worked for a distance of abort 3 miles east and 5 miles west of the town. At the western extremity and near the Carrolena mine, a small town called San Pedro was built. The ruined walls of the houses form a single street, and all is over-

Aug 1, 1912