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By R. A. Bell, R. Schultz, P. G. Hallof

The Ballyvergin area is located in County Clare on the southwest coast of Ireland. It is one of six areas in County Clare in which mining operations were carried out during the last century. The ores mined were high grade Cu-Pb-Ag deposits in the form of small fracture fillings and gash veins in the lower Carboniferous limestones. The zone of primary economic interest is situated on the north limb of a geosyncline which plunges moderately to the southwest. The zones of mineralization previously mined were associated with local structures and folds, and the initial geophysical investigations took the form of reconnaissance induced polarization measurements around, and between, the old mines. This work located an anomaly which, on drilling, resulted in a small extension of the Pb-Cu ore at the Ballyvergin mine. However, a potentially more important zone of mineralization resulted from the drilling of another IP anomaly near Ballyvergin. This wide anomaly was found to be a domal shaped deposit of disseminated chalcopyrite located at a depth of more than 100 ft. The deposit is controlled by local folding in the sediments and is of a type previously unknown in the area. More IP investigations are under way to locate other deposits of the same type. The Ballyvergin area is located in County Clare, about 35 miles northeast of Shannon Airport, near the Atlantic west coast of Southern Ireland (Fig. 1). Interest in the area stems from a number of occurrences of small, but high grade, Pb-Ag deposits. From the summer of 1960 to the spring of 1961, Irish Base Metals carried out a comprehensive exploration program on a 38-sq mile concession in east-central County Clare in an attempt to locate additional deposits of this type. Field operations consisted of geologic mapping, geochemical soil and stream sampling, geophysical surveying and diamond drilling. The geophysical program consisted primarily of detailed induced polarization (IP) surveys in the general vicinity of old mine workings, supplemented by electromagnetic and self-potential investigations. Subsequent diamond drilling of a well defined IP anomaly close to the old Ballyvergin mine disclosed a sizeable deposit of low grade disseminated copper, a type of deposit previously unknown in this area. REGIONAL GEOLOGY Topography: The topography is of the Karst type with low regional relief. The northern parts of the area are covered almost completely with glacial deposits including a large number of drumlins. Elsewhere the overburden is patchy and only moderately deep. A close network of roads makes every part of the area readily accessible, and rail and harbor facilities are available nearby — Fig. 2. Stratigraphy: The area was mapped on a reconnaissance basis by the Geological Survey of Ireland during the latter part of the 19th century at scales of 1 and 6 in. to the mile. Mapping is complicated in

Jan 1, 1962

By M. J. Marcinkowski, D. Koskimaki, A. S. Sastri

THIS is the second in a trilogy of investigations carried out in order to understand the solid state transformations and their accompanying effects on the deformation behavior of near-equiatomic Ni-Ti alloys. The first stage of this effort has dealt with the strictly martensitic structures obtainable in these alloys, i.e., those in which diffusion processes were not involved.1,2 These martensites could be produced either by rapid quenching or by plastic deformation of the originally B2 type phase. The present investigation, on the other hand, will deal with those transformations in Ni-Ti which do involve diffusion. A majority of investigators3-10 have shown that the B2 modification of TiNi, which is stable at elevated temperatures, decomposes into one or both of the intermetallic compounds NiTi2 and Ni3Ti below about 650°C. On the other hand, this has been disputed by several Workers was undertaken in order to resolve this discrepancy, as well as to shed more light on the nonmar-tensitic decomposition of B2 NiTi. EXPERIMENTAL PROCEDURE Sample preparation, fabrication, and examination were the same as those described previously in Ref. 2. In addition to the 50 at. pct Ni (55.06 wt pct) hypoeu-tectoid alloy used previously, a second hypereutectoid alloy containing 54.4 at. pct Ni (60 wt pct) was also prepared for this study. RESULTS AND DISCUSSION The equilibrium diagram for the Ni-Ti alloy system in the vicinity of Ni-Ti is shown in Fig. 1. The solid lines have been established by the work of Poole and ~ume-Ftothery4 whereas the dotted lines are based on findings obtained in the present investigation as described below. Structure and Morphology. Fig. 2(a) shows a bright field transmission electron micrograph of a two-phase structure obtained in a polycrystalline Ni-Ti alloy that was furnace cooled (approx 200°C per hr) from 1050' to about 300°C. Large plate-shaped precipitates can be observed in a matrix which was found by electron diffraction to possess the high temperature B2 structure. A selected area diffraction pattern of the region covered by Fig. 2(a) is shown in Fig. 2(b), while Fig. 2(c) is a detailed schematic interpretation of Fig. 2(b). The B2 matrix reflections are illustrated by squares while those of the precipitate are shown as circles. The d values associated with the precipitate reflections could be determined quite accurately since the reflections from the B2 matrix, for which the lattice constant is known precisely, were simultaneously present in the diffraction patterns. All of the reflections

Jan 1, 1970

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By Thorp D. Sawyer

In June 1914, one week before I was to be awarded my sheepskin in upper New York State, I received a telegram from New York City which read "Can offer you position as engineer in Chile at $115 a month contract for one year. (signed) Chile Copper Co." That night, Friday, I took a sleeper to New York and arrived at the Guggenheim Brothers' company office at 165 Broadway, just as it was opening up on Saturday morning. Saturday was no holiday in that era. Presenting the telegram at the office, I was ushered into a sub-executive's office and shown a mimeographed contract which 1) agreed to pay me $115 per month from the date of leaving New York until I returned, and with travelling expenses both ways, 2) fixed a charge of $46 per month for board and lodging in company quarters, and 3) stipulated a contract term of one year with the right to retain my services for another year if the company so elected. While a bit huffed at the year's "kicker" I nevertheless accepted. I was then told to prepare to leave the following Wednesday (June 17) on a United Fruit Co. steamer for Panama. Objecting that I still had to receive my degree on the 17th and had planned a vacation in Ohio for a week or so…

Jan 12, 1960

By Max W. Bowen, A. J. Weinig

The important part that dissolved oxygen plays in the cyanide treatment of gold and silver ores is commonly recognized by most metallurgists and mill men. But heretofore there has been no simple method on which the mill man could rely for determining the amount of oxygen in the various mill solutions. A few methods are adaptable to the laboratory, such as the gasometric1 determination by actually measuring the oxygen, Winkler's2 iodometric method, and Schutzenberger's3 method, which depends on the reducing action of sodium hyposulfite on a blue solution of indigo carmine; but these are not readily adaptable to the needs of the mill man and cannot be applied to cyanide solutions without modification. The gasometric method is the most accurate but it takes too long to complete a determination. White's4 method (a colorimetric method that depends on the degree of coloration imparted to a solution of pyro-gallic acid in the presence of caustic soda) although much more rapid than any of the methods named, often gives misleading results on account of grading of colors of different solutions, which nearly always contain various kinds of salts. The method herein described was devised for the use of the mill man, the aim being to develop a simple, practical, accurate method. It is a modification of the Schutzenberger method and depends on the reducing

Jan 1, 1925

By Peter R. Morris, Alan J. Heckler

THREE angles are required to specify the orientation of a crystallite with respect to a physical reference frame. The distribution of crystallite orientations in a polycrystal is thus a function of three angular variables. The most widely used experimental techniques for studying orientation in polycrystals lead directly to the pole figure representation, i.e., the distribution of the poles of certain crystallographic planes in terms of two angular variables. In recent years1-5 methods have been developed which permit determination of the (three-angle) crystallite orientation distribution from several (two-angle) pole figure distributions. In this work Roe's method has been applied to the study of orientation in hcp materials. The method is illustrated for commercial purity titanium sheet (Ti-70) which was cold rolled (65 pct reduction), annealed at 1450°F for 3 min, and air cooled. The grain shape was observed to be equiaxed after this treatment. EFFECTS OF PHYSICAL, CRYSTALLOGRAPHIC SYMMETRY In Roe's method the crystallite orientation distribution, w(?,?,F), is expanded in a series of generalized spherical harmonics 11(?,?,F) = E E E W^Zirmtye-tote-in* [l] 1=o ,,,=-I ,,=-I where { = cos 8. The set of Euler angles employed here is illustrated in Fig. 1. The axis for each rotation is denoted by a double arrowhead. The positive sense of each rotation is that of a right-handed screw advancing in the direction of the double arrowhead. The X, Y, and Z directions correspond to the rolling direction, cross direction, and normal direction, respectively. In the initial orientation (10.O), (12.O), and (00 . 1) planes are perpendicular to the X, Y, and Z directions, respectively. The IC/ rotation about the Z axis is carried out first by rotating X into X', Y into Y', and leaving 2 unchanged, i.e., Z' = Z. The 8 rotation about the Y' axis is carried out second by rotating X' into X", 2' into Z", and leaving Y' unchanged, i.e., Y" = Y'. The I$ rotation about the Z" axis is carried out last by rotating X" into X"', Y into Y"', and leaving 2" unchanged, i.e., 2"' = 2". Any specified orientation of the X'", Y'", and Z'" crystal-fixed axis system relative to the X. Y, and Z physical axes (rolling direction, transverse direction, and sheet normal direction, respectively) can be obtained by appropriate IC/, 8, and (F rotations. The Zl,, of Eq. [l] are the Jacobi polynomials, augmented by the square root of the weight function. The Zl,, are symmetric in m,n, i.e., Zl,,= Zlnm. For orthotropic physical symmetry and hexagonal crystallographic symmetry, the coefficients, W!,,, of the series are all real, W!mn = Wzfi, = Wlm~ = Wlfi~, 1 and m are even and n is restricted to 6k, where k = ...,-2,-1, 0, 1, 2, .-.. The determination of the Wlmn from pole figure data has been previously described.'~~ The Zl,, may be written in multiple angle form

Jan 1, 1970

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (I) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1938

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly dzerent stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report l,8x,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1937

By Frank A. Herald

Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and /or commercial value. As to each space in the tabulation, it is either (I) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir. Wile we have not provided a column for showing the thickness of the productive zone, generally the difference between average depth to bottoms of productive wells

Jan 1, 1935

By E. O. Lilge, H. Siebert

A design of a multiple-bomb leaching unit particularly suited for the study of heterogeneous reactions, i.e. sol id-liquid-gas interfaces at high temperatures and pressures is presented. The component parts and overall design are described and illustrated in detail. The system has been tested by a limited number of experiments and found to work satisfactorily. Heterogeneous reactions at solid-liquid-gas interfaces, at high temperatures and pressures, are studied in either autoclaves1'4 or bombs5'9. Autoclaves are usually fairly large vessels which have a stirring arrangement incorporated in the design. Mechanical design limits the use of these vessels to relatively low temperatures and pressures. They are particularly well suited to rate or kinetic studies. Bombs can be designed to be operated at high temperatures and pressures, and are smaller vessels; because of this, stirring arrangements are not easily incorporated. In this paper a multiple-bomb system is described, that has been designed to incorporate the desirable features of both the autoclave and the bomb. The described unit has flexibility for an over all study of leaching. Most of the component units in this assemblage are standard equipment, designed and produced by well known manufacturers. No claim is made to the design of this equipment, and although described in some detail, this is done merely for clarity in the elucidation of the system presented. The general layout of the multiple-bomb assemblage is shown in Fig. 1A and 1B. The basic units in this system are: 1) 6 stainless steel 100 ml bombs (Fig. 4)

Jan 1, 1964

By John W. Bell

IN the introduction to an excellent pamphlet, John Gross1 makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18, 19, 21, 22, 23, 24, 30. 34), concluded that a foundation for the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.1 One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur O. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 2323 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a. true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. STADLER'S HYPOTHESIS WORTHLESS It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left-the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things, that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in fine crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1942

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By P. B. Crawford, W. L. Huskey

A study has been made to determine the effects of random vertical fractures existing in a reservoir matrix on the effective matrix properties and producing characteristics of a well. The study indicated that short vertical fractures may distort the isopotentials by 1 percent in the vicinity of the fracture. A correlation was developed which showed the effect of fracture density on the producing capacity of a well. The correlation indicated that fracture shape had little effect on producing capacity, but that total fracture length was closely correlated with the producing capacity. Effective values of reservoir permeability were found to correlate closely with fracture density when measured parallel to the direction of flow. INTRODUCTION In reviewing the petroleum literature, it is found that in most analytical solutions of hydrocarbon reservoir behavior the assumption is made that the rock is uniform throughout although core analysis and well logging surveys indicate that substantially all reservoirs are heterogeneous and some are fractured. Only in recent years have investigators studied the effects of reservoir hetrogeneity. Russell1 discussed the effect of fractures in reservoirs. The literature indicates that fractures greatly affect the exploitation of man reservoirs. This is described by Elkins and Skov2 and Little-field et al. 3 Several types of reservoir heterogeneity have been studied by unsteady-state methods. In 1959, Landrum et al. 4 showed that transient phenomena in hydrocarbon reservoirs could be studied by thermal models. pickering5 studied the flow of heat in stratified linear reservoirs consisting of plates of different metals separated by sheets of rubber which were suddenly exposed to a low-temperature source at one end. Cotman6 studied both laterally and vertically heterogeneous thermal model reservoirs with special reference to cross flow. Another type of reservoir heterogeneity involves the presence of highly permeable, circular lenses around or near the wellbore which was studied by Miesch7 using a thermal and a steady-state model. Many studies have been made of the effects of induced hydraulic fractures on well performance. 8-10 Work regarding vertical fractures that exist initially in the reservoir was reported by Givens, et al.11 Since there appears to be little published work on the importance and influence on reservoir performance of fractures that exist out in the rock matrix, this study was conducted to determine the effects of vertical fractures on pressure distribution, producing capacity and the effective permeability of the reservoir rock. The analogy between the flow of electrical current through a conducting body and the flow of fluid in a porous medium provides a convenient method of studying various aspects of petroleum reservoirs. For electrical radial steady-state flow,12 For steady-state fluid flow, With the above analogy, it is only necessary to establish the ratio of the values of the electrical units in terms of the corresponding flow units to make the analogy quantitative. The ratios are shown below.

By R. P. Dolan, W. M. Shedd, B. L. Buchanan

Analytical expressions are derived from empirical data relating the basic physical device parameters to the radiation dose. To put in perspective and justify the approach taken, the overall problem and methods of attempted solution of radiation damage to transistors in a missile or satellite environment is briefly examined. The main emphasis is on a new criteria for neutron radiation hardness and the device design implications resulting from using this criteria. Contrary to other derived criteria, the derived bipolar hardness relation depends mainly on the initial lifetime rather than the base transit time. It is shown, that contrary to previously accepted beliefs, the inherent attainable radiation tolerance of JFET's is at least a factor of ten greater than the radiation tolerance ofbipolars. Experimental results on JFET's designed for maximum neutron radiation tolerance are presented. The accuracy, utility, and range of possible validity of various published lifetime and carrier removal damage constants are discussed. It is well known that transistors are subject to damage due to radiation at much lower radiation levels than those which would cause structural damage to a missile or satellite. The three principal categories of radiation damage to transistors are displacement, ionization, and thermomechanical. The main cause of displacement damage is fast neutrons, and the main effects which permanently degrade transistor operation are minority carrier lifetime reduction and carrier removal. A second-order effect is mobility reduction. The main cause of ionization damage is gamma radiation which results in permanent effects due to charge build-up in the oxide and transient effects due to photo-current generation. The transient effects are usually handled by using circumvention techniques in the electronics system. The extent of the transistor degradation due to displacement and ionization damage depends strongly on the transistor type, whereas the extent of thermomechanical damage does not depend on the transistor type, but depends mainly on packaging and metallization which are common to all transistor types. The standard transistor types are categorized in Fig. 1 and typical cross-sections are shown in Fig. 2. The original reason for the designation of the two classes of transistors was that the unipolar operation depends on only one carrier (majority) and the bipolar operation depends on both minority and majority car- riers. The bipolar is then seriously degraded by minority carrier lifetime reduction, whereas the unipolar or field effect transistor is not. One of the two principle classes of field effect transistors, the junction field effect transistor (JFET), depends strongly on carrier removal. However, the insulated gate (MIS) is little affected by either carrier removal or lifetime changes, but is virtually eliminated as a radiation resistant device because of permanent charge build-up in the insulator caused by ionizing radiation. The bipolar and JFET suffer only minor effects due to charge build-up in the oxide passivation when compared1 to the MOS. This is because the active region of the MOS is adjacent to or part of the oxide layer. It is then the bipolar and JFET which are potentially resistant to permanent radiation damage. DERIVATION OF RADIATION TOLERANCE RELATIONS Criteria. The bipolar is by far the most widely used transistor type. The usual criteria for hardening bipo-

Jan 1, 1970

By V. F. Parry, E. O. Wagner

This paper summarizes investigations during 1949 on three pilot plants for drying low-rank fine coal by entrapment in hot gases. Detailed operating results on processing seven coals having moisture ranging from 24 to 62 pet, formulas and data for calculating performance of large units, and general conclusions on the problem of drying fine coal are presented. THIS paper presents a summary of investigations by the Coal Branch of the Bureau of Mines during 1949 on the removal of internal moisture from low-rank coals by processing them in the entrained and fluidized state. A paper on this subject, giving a summary of the early work, was presented at the 1949 AIME annual meeting1 and gave a the- oretical discussion of the time and heat required to dry various sizes of low-rank coal. The investigations on two pilot plants were presented in the foregoing paper. During 1949, three additional pilot plants were built to study phases of the drying problem and to investigate different techniques of handling fine coal in the entrained and fluidized state. The present paper gives operating data on the new units and presents detailed data on the drying of seven coals having bed moisture ranging from 62 to 24 pct. The problem of removing surface moisture from fine coal is principally one of heat exchange and dispersion of the coal particles so that heat can reach the liquid moisture to permit evaporation, and it does not involve the factors of size and time of contact to any great extent. If enough heat can reach the surface of the particles at temperatures higher than 250°F, moisture evaporates almost instantly, and the factors of time and size are of secondary importance compared with the factors of heat balance and dispersion of the coal. Therefore, it does not appear to be necessary to employ a fluidized bed when removing surface moisture, and the most efficient process would be one in which the coal particles are entrained in a hot gas stream of optimum temperature traveling at a velocity that causes the particles to disperse into a low-density phase. When low-rank coals are dried, the fluidized bed is necessary to provide control of time of contact. This is done by adjusting the superficial velocity which controls the density or dispersion of the particles. The density of beds having fluidized properties suitable for drying low-rank coals appears to range from about 5 up to about 15 lb per cu ft. When the density is below 5 lb per cu ft, which represents a low-density phase, optimum conditions for removal of surface moisture should be found, and this requires superficial velocities of about 15 fps. The problem of removing bed moisture from low-rank coals involves consideration of size of coal, temperature, mass flow, heat balance, pressure, time of contact, and method of dispersing the coal in the heating mediums. The experimental work presented here gives data on these factors. Coal sizes up to 1/2 in. x 0 were dried with hot gases having initial temperatures ranging from 1900° to 2400°F. Coal

Jan 1, 1951

By E. O. Wagner, V. F. Parry

This paper summarizes investigations during 1949 on three pilot plants for drying low-rank fine coal by entrapment in hot gases. Detailed operating results on processing seven coals having moisture ranging from 24 to 62 pet, formulas and data for calculating performance of large units, and general conclusions on the problem of drying fine coal are presented. THIS paper presents a summary of investigations by the Coal Branch of the Bureau of Mines during 1949 on the removal of internal moisture from low-rank coals by processing them in the entrained and fluidized state. A paper on this subject, giving a summary of the early work, was presented at the 1949 AIME annual meeting1 and gave a the- oretical discussion of the time and heat required to dry various sizes of low-rank coal. The investigations on two pilot plants were presented in the foregoing paper. During 1949, three additional pilot plants were built to study phases of the drying problem and to investigate different techniques of handling fine coal in the entrained and fluidized state. The present paper gives operating data on the new units and presents detailed data on the drying of seven coals having bed moisture ranging from 62 to 24 pct. The problem of removing surface moisture from fine coal is principally one of heat exchange and dispersion of the coal particles so that heat can reach the liquid moisture to permit evaporation, and it does not involve the factors of size and time of contact to any great extent. If enough heat can reach the surface of the particles at temperatures higher than 250°F, moisture evaporates almost instantly, and the factors of time and size are of secondary importance compared with the factors of heat balance and dispersion of the coal. Therefore, it does not appear to be necessary to employ a fluidized bed when removing surface moisture, and the most efficient process would be one in which the coal particles are entrained in a hot gas stream of optimum temperature traveling at a velocity that causes the particles to disperse into a low-density phase. When low-rank coals are dried, the fluidized bed is necessary to provide control of time of contact. This is done by adjusting the superficial velocity which controls the density or dispersion of the particles. The density of beds having fluidized properties suitable for drying low-rank coals appears to range from about 5 up to about 15 lb per cu ft. When the density is below 5 lb per cu ft, which represents a low-density phase, optimum conditions for removal of surface moisture should be found, and this requires superficial velocities of about 15 fps. The problem of removing bed moisture from low-rank coals involves consideration of size of coal, temperature, mass flow, heat balance, pressure, time of contact, and method of dispersing the coal in the heating mediums. The experimental work presented here gives data on these factors. Coal sizes up to 1/2 in. x 0 were dried with hot gases having initial temperatures ranging from 1900° to 2400°F. Coal

Jan 1, 1951

By F. G. Miller

Earlier studies of the mechanism of flotation showed that coal flotation products are contaminated by composite coal and mineral particles. The mineral matter of these particles has the dual effect of increasing the specific gravity and decreasing the coal surface of the particle available for bubble attachment. The present study showed that these particles are more loosely held in the froth column than the high grade coal particles, especially in the coarser sizes. Consequently, it is possible in the laboratory to produce a secondary concentration of the product by sprinkling the froth product with water to wash these loosely held particles from the froth during formation and recovery. To improve coal flotation, Bethlehem Steel Corp.'s research department has been working on a number of related problems based on both physical and chemical factors. The ideal is of course full understanding of the interrelated effects of both sets of factors. However, detailed studies1 of each physical factor have produced immediately usable results in commercial coal flotation and are providing the basis for our current work on the effect of chemical factors. Since these detailed studies provided the basis for the present investigation of froth sprinkling, their key results are highlighted here. For example, for a highly floatable bituminous coal, particle floatability was shown to be directly related to the percentage of coal surface available for bubble attachment and inversely related to particle mass. The data also underscored that in a given size range the addition of mineral matter to a particle makes flotation more difficult both by adding to the mass of the particle and by decreasing the amount of coal surface available for bubble attachment. Size also affects particle floatability in that as the size of particles of a given specific gravity increases, mass increases and the ratio between coal surface area and mass of the particle decreases. Flotation tests showed that any recovery of the coarsest particles in a coal feed is accompanied by progressively higher recovery of finer and finer particles. Consequently, fine high-specific-gravity particles are recovered with the coarse good coal. As a result, when the entire 14 mesh x 0 size range is processed by froth flotation, the good coarse coal is contaminated with high-specific-gravity fines. It is the small quantities of these fines that must be rejected from the froth product if flotation efficiency is to be increased above its present level. These principles and findings, together with work by Professor V. I. Klassen,' led to the froth sprinkling investigation reported in this paper. Working with Russian coals, Klassen had shown that froth sprinkling washes loosely held refuse particles from the froth and compensates for the water lost in the upper froth layers and increases its stability. As a result, the coal particles are retained in the froth and the loss of coarse coal from the froth is prevented. Decreases in ash of 0.1% to 1.5% were reported by Klassen. Working with a 28 mesh x 0 American coal, the author of the present paper found that single-stage flotation coupled with froth sprinkling produced a product comparable to that obtained by the more expensive method of roughing and cleaning.3 The investigation reported in the present paper expanded study of the effect of froth sprinkling to include each of the standard size fractions of a bituminous coal. The main findings are as follows: (1) For those size fractions between 48 mesh and 150 mesh, froth sprinkling produces a marked reduction in both sulfur and ash. In the case of those sizes coarser than 48 mesh, while this reduction is not as significant, the additional benefit of shorter retention time is still a plus for froth sprinkling. Furthermore, when froth sprinkling is coupled with normal fast flotation, the product purity approaches that obtained by starvation reagent feeding, i.e., gradual feeding of flotation reagent to float the recoverable coal from the pulp slowly in several increments. The specific results for these two size groups are: (a) 14 x 48 Mesh. By using froth sprinkling with fast flotation, product sulfur can be reduced to a level

Jan 1, 1970

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By H. Macpherson

Durhm has a well earned reputation for supplying some of the finest coking caals in the world. The caals, in general, vary in rank from 301 to 501/2. Durham has traditionally produced foundry coke for the major proportion of the foundries in Great Britah. Durham coals can be described as clean, soft coals, which yielded, with the old hand methods of coal getting, low ash small coal because the extraneous shale was normally harder than the coal and occurred in larger pieces. Under these conditions, with a plentiful supply of cheap labor, it used to be sufficient, at most collieries, to hand clean the large sizes of coal which could then be remixed with the untreated small coal to produce carbonization coals, ready for the coke ovens, at under 5 pct ash. With the introduction of mechanical methods of coal mining, the coal gradually required more cleaning. The first method adopted to resolve this problem was the introduction of pneumatic dry cleaners for the small coal. Although such machines had little effect on the fine coal (say below 1/8 in.), they could clean the intermediate sizes of coal. This, coupled with hand cleaning the larger sizes above 1-1/2or 2 in., resulted in a combined run-of-mine mixture below 6 pct ash, capable of maintaining the quality and reputation of the cokes produced. In more recent years, the intensification of mechanization and power loading, coupled with gradual exhaustion of the cleaner seams, has created the need for a more complete method of coal cleaning. This particularly applies in the fine sizes (say below 1/50 in.) which normally vary, under present day conditions, between 15 and 35 pct ash and are much too dirty to be included in the raw state in a carbonization mixture. This pronounced change has been accelerated because legislation controlling the dust conditions of mine airs for the prevention of pneumoconiosis has resulted in tk~e extensive use of water underground and a consequent increase in moisture content of the run-of-milie output. The presence of damp fine coal decreast the efficiency of prescreening and dry cleaners, so that this type of preparation for low ash coking coals is decreasing, although it is still used satisfactorily for industrial coals in the medium ash range. Table I shows the gradual increase in mechanization, the reduction in manpower, the increased use of explosives per ton of coal extraction, and the increase in the proportion of coal cleaned by mechanical means in Great Britain. Although similar figures are not available for Durham Div. until after the date of nationalization of the coal industry, it is probable that the increase in mechanical cleaning, particularly by dry cleaners, was more marked in the Durham collieries than elsewhere in the country. As dry clealiers were replaced by coal washeries in the Gritish ccal industry, no special attempts were made to recover the slurry, with the result that large outflows of dirty water were allowed, deposits of slurry came in to lagoons and neighboring streams, and a proportion of fine material was lost from the coking coal. This position, coupled with the higher moisture of the washed coking coal, resulted in adverse effects on coke oven throughputs and coke quality. It is now realized that the natural coal fines are an essential ingredient of coking coals in obtaining the correct coke structure in metallurgical cokes. This, together with economic pressure, led to the introduction of flocculation and filtration plants for the recovery of slurries, and later, when the ash contelits of the filter cakes were too high, to the introduction of froth flotation equipment. After this position had been reached, the tailings from the froth flotation pIants were, in many cases, still allowed to constitute an undesirable effluent. Recent legislation on river pollution has changed this picture; it is now necessary to provide a circuit which is completely closed so far as solids are concerned. The gradual increase in the coal cleaned by wet methods and froth flotation in Durham Div, is shown in Table 11. It is now an accepted feature of new Washeries that. froth flotation should be an integral part of the washing process from the initial installation of the plant.

Jan 1, 1962