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By J. B. Dyess

TARNISH films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper .2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen. sulphide in air to form the various oxide-sulphide films studied. The comparative resistances afforded by (1) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of T= MX10 8 2D X 96,494 X 103 (a) where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angström units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values2 of t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By Jesus P. Manzano

The report of which this paper is a summary was made in 1890 for the Compania Investigadora Mexicana y Americana. Since the region examined covers 900 sq. kilom., chiefly of wooded arid rocky hills, almost without roads, and for the most part uninhabited, While the examination had to be made in two months, of which period more than 15 days were continuously rainy, I need not say that this account is not complete and thorough. I. Geography and Topography. The center of this zone, 19 kilom. SW. of San Luis Potosi, is situated in lat. 21° 24' N., and long. 2° 3' W. of Mexico City. The altitude ranges from 1866 m. (that of San Luis) to . 2816 m. (that of the Realito mountain), in the Sierra de Sail Luis. The topography is hilly—partly wooded, partly bare. The principal more level areas are the Bledos valley on the south, and portions of the haciendas of Tepetates, San Fran cisco and Santiago, on the west. The water-supply is scanty. The two streams that cross the Zone, the Santiago and Bledos rivers, carry water nearly the year through, though much reduced in the dry season. Other streams are torrents of less importance. All the waters of the valley and Sierra of Sail Luis arc absorbed or sink, not passing beyond Soledad de los Ranchos. The Continental di vide is within the Zone, some waters going west to the Pacific, others east to the Gulf of Mexico. II. Geology. Concerning the geology of this district I condense the fol lowing from the memoir, Las Minas de Guanajuato, prepared for the Minister of Fomento by Senor Pedro Lopez Monroy, mining engineer, with which I am entirely in accord. He says, ill substance:

Jan 1, 1902

By William E. Ford, Edward Salisbury Dana

Secondary Twinning. - When there is reason to believe that the twinning has been produced subsequently to the original formation of the crystal, or crystalline mass, as, for example, by pressure, it is said to be secondary. Thus the calcite grains of a crystalline limestone often show such secondary twinning lamella?. The same are occasionally observed (Ilc, 001) in pyroxene crystals. Further, the polysynthetic twinning of the triclinic feldspars is often secondary in origin. This subject is further discussed on a later page, where it is also explained that in certain cases twinning may be produced artificially in a crystal individual - e.g., in calcite (see Art. 282).

Jan 1, 1922

Executive A R LEDOUX, Chairman ARTHUR S DWIGHT CHARLES F RAND E P MATHEWSON J V W REYNDERS Membership E DEGOLYER, Chairman W Y WESTERVELT, Vice-chairman WILLIAM H BASSETT H G MOULTON C MINOT WELD Finance WALTER H ALDRIDGE, Chairman GEORGE D BARRON GALEN H CLEVENGER Library GEORGE C STONE,' Chairman JOHN H JANEWAY ALEXANDER C HUMPHREYS, ROBERT LINTON FREDERICK F SHARPLESS

Jan 1, 1923

By Martin G. Castro, Renato G. Bautista, Morton Smutz

During the last 25 years, multistage mixer-settlers have been used extensively for liquid ion exchange work. The mixer-settler has the advantage of being a compact device in which a large number of stages can be assembled in a relatively small area. They are particularly advantageous for the separation of rare earths. Most of the adjacent rare earths have separation factors which are near one, which means that a large number of stages are needed to produce a good separation. When two elements (m, n) are extracted simultaneously, the separation factor (ßm, n) is defined as: [ ] where Ym, Yn are the molarities of the respective elements in the organic phase and Xm, Xn, are their molarities in the aqueous phase at equilibrium. The industrial consumption of rare earth oxides rose to over 6800 tons in 1968, an increase of 33% over 1967.1 The increased production and demand for rare earth and lanthanum chlorides for petroleum cracking catalysts was one of the principal factors in this increased consumption of rare earths. In 1968 approximately 59% of the rare earth oxides produced were used for gasoline cracking catalysts in the form of rare earth and lanthanum chlorides. There was also an increase in the sales of lanthanum oxides for use in optical lenses and in fiber optics. The future looks good for the rare earth industry. The rare earths can be expected to be used in many new products which are being developed. Until the late 1950's tributyl phosphate (TBP) was the principal solvent used in rare earth liquid ion exchange. In 1957 Peppard3 reported the use of di (2-ethyl-hexyl) phosphoric acid (D2EHPA) as a solvent for separating the rare earths. Rare earth separation factors of up to 2.5 were obtained in nitrate and chloride systems while the maximum separation factor using the

Jan 1, 1972

By Ray W. Ballmer

"For his leadership in developing and managing large, complex, and technically innovative mines, particularly the outstanding and successful Bougainville mine and for his lecture, 'The Moving Targets of Mine Development '. " Recipient of the 1981 D. C. Jackling Award

Jan 1, 1982

By T. K. Smith

The comments contained in the discussion of the paper concerning the prediction of fracture gradients are of considerable interest, since the subject is of a very controversial and timely nature. It is regrettable and Fairhurst2 contradicts the author's statement in the third paragraph of Other Applications. These references create significant doubt that Eaton's Eq. 1 predicts fracture pressure during the injection of fluid into old wells. 3. No evidence is presented in this paper to support the author's Conclusions 2 and 3. While an empirical coefficient related to back-calculated field data is correlated with depth (Eaton's Fig. 4), there is no reason to suspect that this coefficient might be the Poisson's ratio of the various formations involved. 4. Until the field data supporting the empirical approach proposed by the author are presented and evaluated, the accuracy claimed in Conclusion 5 is without substantiation. References 1. Geertsma, J.: "Problems of Rock Mechanics in Petroleum Production Engineering", Proc., First Intl. Symposium on Rock Mechanics, Lisbon (1966) 585. 2. Haimson, B. and Fairhurst, C.: "Hydraulic Fracturing in Porous-Permeable Materials", I. Pet Tech. (July, 1969) 811-817. that the comments are those of a critic and do not offer an alternative and better method for the prediction of fracture gradients. Nevertheless, a reply is in order.

Jan 1, 1970

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to flocculation of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves.

Aug 1, 1956

Jan 1, 1971

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By G. Gabra

The kinetics of acidified thiourea leaching of pyrite concentrate was investigated at temperature ranging form 20 °C to a 60 °C. The effect of various parameters on the dissolution rates are discussed. The gold extraction was found to be zero and first orders with respect to Fe (111) and thiourea concentration, respectively. The order of the reaction with respect to sulfuric acid was found to be zero. The activation energy was determined from the Arrhenius plot as 2,039 kcal mole -1 (for a freshly prepared acidic solution containing Fe (111) as the oxidant and at 800 rpm stirring speed. This relatively low activation energy value suggests that the gold extraction is controlled by a-physical phenomenon. Under optimum conditions, more than 90% of gold has been dissolved in about 30 min. and 95% in 60 min. Attempt to recover gold from thiourea solution using active carbon is also discussed.

Jan 1, 1984

By Warren E. Wilson

THE transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. ENERGY. REQUIREMENTS Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: [Solids load in terms of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m, Mass per unit volume of liquid by ml Mass per unit volume of mixture by m,,, We then have as an expression for the solids load: W = pQm¬] The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1945

By E. Hornbogen

The deformation mechanisms of a iron-phosphorus alloys were compared at 20oand —196°C. Alloying with phosphorus increases the resistance to slip, but has little effect on the resistance to twinning. The stress for onset of twinning is nearly independent of temperature, but there is an increasing tendency for cleavage along (112) twin boundaries with decreasing temperature and increasing phosphorus content. FIVE iron-phosphorus alloys and one high-purity iron (0.004 pct C, 0.004 pct N, 0.05 pct O) were vacuum melted and cast, then homogenized for 6 hr at 1100oC and water-quenched. Single crystals were cleaved from the coarse grains produced in this manner. The hardness was measured* on polished (100) surfaces of the crystals at 20" and -196°C. Laue back-reflection patterns indicated a deviation of not more than 3 deg from coincidence of the {100} plane with the surface. The deformation mechanisms were studied by relief effects on the polished surfaces. Yield points in compression (0.5 pct offset) were measured with polycrystalline material. At 20°C the addition of phosphorus to a iron leads to a change from slip to twinning as the main deformation mechanism, Figs. 1(a), (b). Between 2 and 4 at. pct P slip and twinning occur simultaneously. In alloys with more than 4 at. pct P twinning is the main deformation mechanism and slip was observed only in the neighborhood of twin intersections. All cracks at 20oC were on (100) planes, some initiated by twins.' From measurements made at-196oC, hardness and yield points of all the alloys were nearly constant and the same as the hardness of high phosphorus alloys that deformed by twinning at 20°C, Figs. 2 and 3. In the high-purity iron, plastic deformation at -196°C occurred by both slip and twinning, but deformation in the iron-phosphorus alloys appeared to be entirely by twinning. In the high phosphorus alloys a large number of cracks formed along the (112) twin boundaries and at intersections of twins, in addition to the (100) cleavage, Fig. 1(c). DISCUSSION In , iron, plastic deformation can occur either by slip or by twinning, depending upon composition,

Jan 1, 1961

By Louis A. Carapella, William E. Shaw

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By William E. Shaw, Louis A. Carapella

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By Willard P. Ward

The numerous direct processes which have been patented and brought before the iron-masters of the world, differ materially from that now introduced by Mr. Wilson. After a careful examination of his process, I am convinced that Mr. Wilson has succeeded in producing good blooms from iron-ore, and I think that I am able to point out theoretically the chief reasons of the success of his method. Without going deeply into the history of the metal, I may mention the well-known fact, that wrought-iron was extensively used in almost all quarters of the globe, before pig or cast-iron was ever produced. Without entering into the details of the processes by which this wrought-iron was made, it suffices for my present purpose to say that they were crude, wasteful, and expensive, so that they can IE employed to-day only in a very few localities favored with good and cheap ore, fuel, and labor. The constructiou of larger furnaces and the employment of higher temperatures led to the production of a highly carbonized, fusible metal, without any special design on the part of the manufacturers in producing it. This pig-iron, however, could be used only for a few purposes for which metallie iron was needed; but it was produced cheaply and with little loss of metal, and the attempt to decarbonize this product and bring it into a state in which it could be hammered and welded was soon successfully made. This process of decarbonizatioa, or some modification of it, has successfully held the field against all, so-called, direct processes up to the present time. Why ? Because the old-fashioned bloomeries and Catalan forges could produce blooms only at a high cost, and because the new processes introduced failed to turn out good blooms. Those produced were invariably "red-short," that is, they contained unreduced oxide of iron, which prevented the contact of the metallic particles, and rendered the welding together of these particles to form a solid bloom impossible. The process of puddling cast-iron, and transforming it by decarhonization into wrought-iron has, as everybody knows, been in successful practical operation for many years, and the direct process referred to so closely resembles this, that a short description of the theory of puddling is not out of place here.

Jan 1, 1884

Jan 1, 1968

By H. E. Montgomery

Engineering trends for some years have been toward higher temperatures, both in process work and in steam generation. Progress in design has been dependent upon the development and evaluation of suitable alloys. Elementary knowledge of the limitations of copper-base alloys indicate their unsuitability for the higher ranges of operating temperatures; say, for steam to 950°F. Emphasis upon the more severe conditions perhaps is a reason why more complete evaluations have not been made for copper-base alloys over their range of suitability. However, the few studies made show clearly the need for more accurate evaluations. Some copper-base alloys long looked upon favorably because of superior room-temperature properties are not as desirable as some others perhaps not so "strong" and "hard," as measured by usual acceptance tests. Load-carrying capacity and structural stability arc two important factors. Structural stability as influenced by temperature, by presence of corrosive media, or by the effects of stress itself, frequently is a limiting factor. An early reference to creep properties of the cast copper-base alloys is that of Brown1 (Admiralty gun metal, Cu 87.5, Sn 10.1, Zn 2.3 and Pb 0.08). His tests were similar to present-day stress-rupture tests without measurement of creep elongrttion. Loading was in steps with usually 24 hr. between steps, and continued until failure. He advocated a "useful strength value" of 61/2 tons (I4,560 Ib.) per sq. in. at 572°F. (300°C.). A specimen broken in 1/2 hr. at 572°F. had a strength of 21 tons (26,880 Ib.) per sq. in. The strength values as determined by 1/2-hr. tests and those by the longer stress-rupturc start to differentiate at 392°F. (200°C). This is the temperature at which time at load began to play an important part. Bolton, Price and Hebemann2 give creep curves on 88-10-2 (A.S.T.M. B-60, CU 88, Sn 10, Zn 2) and steam or valve bronze (A.S.T.M. B-6I, Cu 87.50, Sn 6.00, Zn 3.75, Pb 1.70) at 500°F. Direct comparison of the two alloys under 7500 lb. per sq. in. stress showed the steam bronze (A.S.T.M. B-61) superior in creep strength to the 88-10-2 (A.S.T.M. B-60). The steam bronze shows no creep after 700 hr. (1540-hr. test). The 88-10-2 shows a rate of about 7.0 per cent in 100,000 hr. over the last 700 hr. of the test. Creep curves on the steam bronze are also given at the same temperature (500°F.) with loads of 6500 lb. per sq. in. and 8000 lb. per sq. in. These indicate "creep strengths" (creep rate within I per cent in 100,000 hr.) in excess of 8000 lb. per sq, in. for this alloy. It was found that higher percentages of tin are detrimental to creep resistance. This is caused by the presence of or formation during test of considerable alpha-delta eutectoid in the higher tin alloys. Bolton also states that the high

Jan 1, 1945