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Jan 1, 1968

The pellet plant, built by Dravo Corp, in Groveland, Mich., for the Hanna Mining Co., is now in full operation. Although using jasper, a type of iron ore with low iron content (approximately 28% Fe), the plant has a rated capacity of 1,250,000 tans of pellets per year. In its four years of existence, the nearby concentrating plant has seen its capacity increase from 700,000 tons to 1,500,000 tons a year as part of a major expansion program at Groveland. Utilizing the Dravo-Lurgi continuous grate process, the pellet plant produces %a-in. pellets of more than 60% iron content. The fully-hooded pelletizing grate, largest in the U.S., is 9 ft. 10% in. wide and 223 ft. 1% in. tong over 34 windboxes, with an effective hearth area of 2195 sq. ft. Drying, firing, and cooling functions are all carried out on this single piece of equipment.

Jan 4, 1964

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 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 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 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, 1968

By G. R. Mansfield

THE geologic structure of the Idaho phosphate field has an important bearing on the classifica-tion and the exploitation of the lands that contain phosphate. Maps and structure sections1 recently made available show that the phosphate is mainly preserved in downfolded or downfaulted areas. Since the phos- phate beds are generally rather soft and lie between harder and thicker formations they have been forced to adjust themselves to these formations during epochs of disturbance of the earth's crust, so that they are frequently affected by minor folds and by faults which may help exploitation by producing undue thickness at certain places or may hinder it by cutting out the phosphate at other places where according to expecta-tion it should be present. A particularly important structural feature which affects both the distribution and the exploitation of the phosphate beds is the great Bannock overthrust by which one or more slices or blocks of the earth's crust have been pushed over other blocks like ice cakes on a pond. Thus in this region a great flap of folded rocks lies across other rock structures for a distance of approximately 35 miles. Most of the commercially accessible phosphate deposits, shown in the maps that accompany the report cited, are in this flap, which con-stitutes the upper block of the overthrust. In some places, however, the phosphate in the lower block is also accessible. In both blocks post-phosphate rocks exposed at the surface here and there indicate that phos-phate beds may lie at greater or less depth below. The presence of the Bannock overthrust beneath much of the area reported is known by the occurrence of windows in the upper block both within the quadrangles mapped and in areas farther west. The portions of the lower block exposed in these windows show stratigraphic dis-cordance with the surrounding formations. The depth of the fault plane at most places, however, can be told only by drilling or actual mining. Some of the folds in the upper block are relatively deep and it seems fairly certain that the phosphate that may originally have been present in their deeper parts has been removed by thrust faulting. The estimates of phosphate reserves in folds liable to be affected by the Bannock overthrust may therefore need ultimate revision depending on the depth of this fault plane, as it may subsequently be ascertained.

Jan 1, 1928

By Ivan Simon, R. K. McConnell

Anticipating the availability of tiltmeters suitable for use in boreholes, this article proposes a method of using one or more of these meters to determine in situ stress distribution before and after mining operations. Several ways of using relief techniques to measure in situ stresses in rocks have been developed. These techniques, summarized by Merrill,1 involve measuring deformations which take place when a specimen of rock is wholly or partially isolated from the stress field in the surrounding rock. Measurements of rock deformation caused by stress relief from mining operations can, in principle, also be used to estimate in situ stress distributions. Müller2 has mentioned experiments being carried on in Austria with a "deformation indicator" to determine the tilting of holes drilled before a mine opening is made. Similar work using borehole extensometers has been reported by Potts? and Duvall4 has called attention to the possible use of tiltmeters in making these measurements. Considerable attention is now being paid to the use of tiltmeters in detecting rock deformation associated with fault movements, earthquakes, earth tides, etc. The instruments used for these measurements have usually been of the mercury tube, water tube, or quartz fiber type, but because of their large size, and/or fragile nature, such instruments would not be suitable for use in mining stress measurements. Recent instrumentation developments, however, give promise that rugged, sensitive tiltmeters small enough for use in boreholes may soon be available.' In anticipation of these developments, this article presents a number of calculations of the possibility of using one or more tiltmeters emplaced in a drill hole prior to mining operations to determine the in situ stress distribution both before and after a mining operation. Consider point p (x, z) near a tunnel of radius a

Jan 1, 1969

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 J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

By George M. Fowler, J. P. LYDEN

T HE relationship of geological structure to orebodies and to the great masses of chert in the Tri-State mining district is of such significance that it prompts a brief recital of the existing information regarding the various periods of structural deformation. We began to note a relationship between structure and orebodies early in our studies of the field, and further work revealed a like relationship of structure to the great masses of chert so commonly associated with the ore-

Jan 1, 1934

By B. N. Das, P. A. Beck

THE o phases have a complex tetragonal structure with Lo/ao = 0.52 and 30 atoms per unit cell.1 A large number of such phases are now known to occur in various binary systems of the transition elements and they exhibit the following typical features: 2,3 The composition of binary o phases is variable, ranging from approximately A4B to ABI. With only a few exceptions, in the o phases the A-ele-ment comes from the V- or Cr- group of the periodic table, while the B-elements are from the Mn-, Fe-, Co-, or Ni- group. In the first long period the corresponding o phases of the V- and Cr-series have approximately the same compositions. However, as the B-element changes from Mn to Fe to Co to Ni, the mean composition shifts monotonously toward higher A-contents.2-4 For example, if the mean compositions of the various o phases with vanadium are compared with each other, the composition shift mentioned above becomes plainly visible: V 30Mn0 80 Vo.45Feo..,, Vo .,Coo. 45 and Vo.5Nio.3. Similiar composition shifts, although not the same composition values, were observed in u phases formed by second and by third long-period transition elements.3'4 This behavior, very characteristic of o phases, is in rather sharp contrast to the usually quite well-behaved stoichi-ometry of the Laves phases. In the latter, the AB2 stoichiometry predominates, with A the large atom and B the small atom.= The p phase occurs in the four binary systems of Mo or W with Fe or Co. On the basis of their crystal structure determination, Arnfelt and westgren6 ascribed to the p phase in the Co-W system the ideal composition W,Co7. Since all four binary pphases have nearly the same composition, it would seem quite plausible that some definite stoichiometry such as A6B7, might be characteristic of this phase, as AB2 is of the Laves phases. On the other hand, it has been noted,7 that the phases occur at average electron concentrations near to those at which the various cr phases are found. Also, it has been pointed out by Shoemaker and associates8 that structurally the a phases and the p phases are somewhat related to each other; both of these structures may be described in terms of suitable stackings of quasi-hexagonal layers'of atoms. By studying a suitably chosen ter- nary phase diagram, one might expect to be able to find out which one of the two conditions, the analogy with the o phase or the constant ratio between the number of large atoms and the number of small atoms in effect governs the behavior of the p phase. Several isothermal sections of ternary systems containing o phases have been investigated. In all cases where two binary o phases occur, these were found to be connected b a more or less straight ternary o phase field.7' '10 Such elongated o phase fields were also found in ternary systems in which only one of the limiting binaries is known to contain o phase. In this manner a latent o forming tendency could be detected and the virtual composition of a "binary o phase", which does not actually occur as such was approximately determined by extrapolation. The behavior of the phases, including their composition shift, is analogous to that of the classical electron compounds, as described by Hume-Rothery.11 In order to decide whether the p phase is essentially a "size compound" like the Laves phases, where a fixed stoichiometric ratio is quite generally maintained between the "large atoms" and the "small atoms", or whether the p phase is typically an "electron compound" in the same sense as ois, it was decided to investigate an isothermal section of the Mo-Mn-Co system. The Mo-Co system12 and the Mo-Mn system13 each are known to have a binary o phase. It could be therefore expected that a ternary o phase field will connect these two binary cr-phase fields. The p phase is known to occur in the Mo-Co system. If the p phase should turn out to form an elongated phase field extending deep into the ternary system, the following considerations mighto apply. The atomic radius of manganese (1.314for C.N.12) is between the va,lues for Mo (1.40Afor C.N.12) and for Co (1.26Afor C.N.12). If it is assumed that p is a "size compound", and that Mn is substituting for the smaller Co atoms in the p-structure in the ternary system, the y-phase field might be expected to extend parallel to the Mn-Co binary line. If Mn is substituting for the large Mo atoms in the p-structure, the p-phase field may be expected to extend parallel to the Mn-Mo binary line. On the other hand, if the p-phase turns out to be an "electron compound" like o, the ternary p-phase field should extend parallel to the ternary o -phase field connecting (Mo,Mn)owith (Mo, Co) a

Jan 1, 1961

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

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 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 C. H. Li, R. D. Carnahan, R. J. Stokes, T. L. Johnston

When silver chloride deforms by pencil glide at temperatures of 26ºand 72°C, grain size has no effect upon the proportional limit and the material necks down to a knife edge under tension. At -196ºC, deformation takes place on fewer slip systems to produce straight slip traces, the flow stress becomes sensitive to grain size and fracture occurs by cleavage from an intergranular source without any reduction in area. THERE are significant differences between the appearance of the slip bands formed in silver chloride and in the alkali halides at room temperature. The bands in sodium chloride, e.g., are fine and geometrically straight, whereas in silver chloride they are coarse and wavy.' Such differences in the slip behavior prompted us to inquire what the effects of grain boundaries might be on the mechanical properties of these solids. As an introduction to a general study of ionic poly-crystal behavior, we have investigated the effect of grain size on the stress-strain relationships in silver chloride at different temperatures. We have chosen silver chloride chiefly because polycrystals can be easily prepared free from cracks and macroscopic voids by conventional techniques. Moreover, as we shall see, the slip behavior can be readily modified by changing the temperature. It will be shown that the effect of grain size on the yield stress of silver chloride is strikingly dependent upon the temperature of deformation and that this temperature effect comes about through a change in the number of slip systems which operate at the onset of plastic flow. EXPERIMENTAL PROCEDURES Polycrystalline tensile specimens were made by recrystallizing cold-rolled AgCl sheet. Thirty-gram quantities of AR grade silver chloride powder were melted in a low heat capacity furnace, cast into cylindrical forms 3/4 in. in dim and approximately 1 in. in length and then extruded with a 16:l reduction ratio into rods 3/16 in. in dim. Extrusion temperatures were varied from room temperature to 350°C. In order to impart various degrees of cold'work to the extruded rod. All extrusions were then cross rolled to sheet 0.040 in. in thickness at room temperature and machined to form tensile specimens having a gage length of 0.750 in. with a width of either 0.250 or 0.145 in.* Annealing was carried out in an air oven at 200°C for periods up to 20 hr. specimens having average grain diameters ranging from 0.024 to 0.40 mm were prepared by varying the extrusion temperature and annealing time in the conventional manner. To obtain specimens with grain sizes larger than 0.40mm, lightly deformed thin prisims of silver chloride single crystals (supplied by Harshaw Chemical Co.) were recrystallized. Grain size determinations were made by an intercept method and revealed that the grains were equi-axed. Laue back-reflection X-ray patterns showed little tendency to form a preferred orientation texture. Specimens which were to be used for the slip band studies were polished by immersion in fresh boiling concentrated NH,OH for 60 sec. They were then etch polished for 10 sec on each side by hand lapping on a stationary velveteen lap wetted with a dilute Hypo solution (5 g of Kodak Acid Fixer in 100 cc H20). Finally the specimens were rinsed in warm water and alcohol, blown dry and carefully mounted in the tensile machine for testing. Tensile tests were performed at three temperatures, namely, 26º, -72º, and -196°C. A screw-driven hard tensile machine was used at a constant strain rate of 0.006 in. per in. per min. Loads were determined with a light- proof ring fitted with A-18 strain gages and extensions were measured with a 0.0001 in. dial gage. Constant level baths of alcohol with dry ice and liquid nitrogen were used to maintain the two lower test temperatures. EXPERIMENTAL RESULTS Reproducibility—In view of the light sensitivity and reactive nature of silver chloride, it was necessary to determine whether reproducibility depended upon either exposure to light or to the condition of the surface. However, during the course of the work it became clear that variation of laboratory lighting

Jan 1, 1962