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By D. P. Pope, T. Vreeland

Observations of dislocations in zinc using Berg-Barrett X-ray micrography confirm the validity of a dislocation etch for (1010) surfaces. A technique for measurement of the depth in which dislocations can be imaged in X-ray micrographs is given. This depth on (0001) surfaces of zinc was found to be 2.5 µ using a (1013) reflection and CoKa radiation. BUCHANAN and Reed-Hill (B & RH) have recently questioned the ability of a dislocation etch to reveal all of the basal dislocations which intersect (1010) surfaces in annealed zinc crystals.' This etch was developed by Brandt, Adams, and Vreeland who conducted a number of different experiments to check its ability to reveal dislocations.2,3 B & RH prepared (0001) foil specimens for transmission electron microscopy from annealed crystals and observed dislocation densities of about l08 cm per cu cm in the foils, while the etch indicated densities of the order of l04 cm per cu cm in their annealed crystals. As this etch has been used in a number of studies of dislocations in zinc, it is of considerable importance to reassess its validity in the light of the B & RH results. The X-ray work reported here was undertaken to check the ability of the etch to reveal dislocation intersections on (1070) surfaces of zinc. The X-ray technique was chosen for this check because it could be applied to the as-grown crystals with a relatively small amount of specimen preparation. We believe that the possibility of accidental deformation in preparation of the bulk specimens is considerably less than that for thin foil specimens suitable for transmission electron microscopy. Unfortunately, basal dislocations are not visible on Berg-Barrett topo-graphs of (1010) surfaces, which are the surfaces on which the etch is most effective. Therefore, a one-to-one correspondence between the etch and X-ray observations could not be made. Basal dislocations near (0001) surfaces have been observed by Schultz and Armstrong4 using the Berg-Barrett technique, but they did not report the as-grown dislocation density observed in their crystals. We have applied the X-ray technique in this study to surfaces oriented from 1 to 2 deg of the (0001) to determine the basal dislocation density, and have compared this density with that observed using the etch on a (1070) plane of the same crystal. The X-ray observations permit determination of the depth in which basal dislocations can be observed under the diffracting conditions used. SPECIMEN PREPARATION High purity zinc crystals are very soft, so a good deal of care must be exercised in the preparation of observation surfaces. As-grown crystals approximately 2.5 cm in diam and 20 cm long were acid cut into 1.25 cm cubes. A thin slab was cleaved from an (0001) surface to produce an accurately oriented reference surface on the specimen. Some of the cubes were examined in the as-machined condition while some were annealed in argon at 410°C for 2 hr. Heating and cooling rates were less than 2°C per min. Some of the specimens were scratched on a (0001) surface with a razor blade to produce fresh dislocations. Approximately 2 mm of material was acid lapped from one face of a cube to produce a surface oriented between 1 and 2 deg from the basal plane and parallel to the [1210] direction. A (1070) surface was also acid lapped. The lap used a 1 to 3 pct solution of HN03 in water to saturate a soft cloth which was backed by a stainless steel plate. The cloth was moved over the crystal surface at a rate of 20 cm per sec while a normal force of about 4 g was maintained between the cloth and the specimen. As-lapped surfaces were examined as were surfaces which were chemically and electrolytically polished after lapping. The small angle between a lapped surface and the (0001) plane was measured to 0.1 deg using a Unitron microgoniometer microscope (the cleaved surface was used as a reference in this measurement). The microscope was modified so that the intensity of reflected light could be continuously monitored on a meter. This modification produced nearly a ten-fold increase in the reproduceability of orientation readings. OBSERVATIONS The Unitron Microgoniometer observations indicated that the lapped surfaces had a terraced structure with the terraces quite rounded and spaced about 0.1 mm in the [1010] direction. The maximum change in slope between terraces was 0.25 deg, indicating a terrace height of about 0.1 µ. A Unitron measurement of the average angle between (0001) and a lapped surface was checked by micrometer measurement of the specimen and found to agree within 0.1 deg. The Berg-Barrett micrographs using (1013) reflections and CoKa radiation5 revealed subboundaries, short dislocation segments, spirals, and loops near the surfaces which were oriented from 1 to 2 deg of the (0001). Micrographs of surfaces prepared by lapping appeared very similar to those of the chemically and electrolytically polished surfaces. The loops and spirals were not extinct in (1013) or (0002) reflections, indicating that they have a nonbasal Burgers vector. Extinctions of the short, straight dislocations indicated that they belonged to an (0001)(1210) system. Fig. 1 is an example of a micrograph which shows a subboundary, and dislocation segments which are pre-

Jan 1, 1970

Ore deposits of commercial grade are local concentrations of great rarity when considered in relation to the area of unmineralized land surfaces, and they must therefore be considered as the products of exceptional and complex conditions. The data collected from a great number of individual deposits are sufficient to permit certain broad generalizations in regard to the conditions favorable to ore deposition which even numerous exceptions do not invalidate. The broadest general relation of ore deposits is with intrusive rocks, and while there are notable exceptions, the great majority of ore deposits have a visible or closely inferred connection with intrusive rock masses. Conditions that permit the dissipation of the ore-bearing vehicles do not permit the concentration of metals in deposits; the prime factor to consider in this connection is that structural conditions must be such as tend to concentrate and not to dissipate the ore-bearing solutions. The disadvantage of extrusive rocks is at once apparent; any metals the magma may have contained are dissipated at the surface and are lost; with the exception of tiny vugs and cracks in quickly cooled flows, no concentrations of metals are known in extrusive rocks, and the lack of confinement and quick cooling apparently do not permit extrusives to exert mineralizing effect upon the rocks with which they come in contact. The close mineralogical similarity between extrusives and intrusives, and the great difference in mineralizing power is a proof of the ease with which magmas part with their metallic content, and of the mobility of the ore-bearing vehicles in comparison with the parent magma.

Jan 1, 1932

By F. E. Calkins

THE following presentation of the more important accumulated facts and probabilities involved in copper ore deposition is based on my experience in examination work and study of the extensive litera-ture of the subject; to make personal mention of all sources of information would require the naming of a small army of able geologists and other investigators who have contributed to, building up the science. I have tried to present the salient features of the subject in logical order and condensed form, and to point out the relative importance of processes involved. Doubt-less many geologists could suggest some changes and many additions. ORIGINAL SOURCE The original source of all copper was in the earth's interior; it has been brought to the outer part of the earth, within reach of man, in three ways: (1) By intrusions and flows of basic igneous rocks containing copper in minute quantities, presumably as silicate or sulfide. No orebodies have been formed by this method. (2) As segregations within intrusive igneous rocks, the copper minerals having solidified at the same time as the rock itself. The few deposits known to have been formed in this manner have been of little or no importance. The oft quoted Sudbury nickel-copper deposits are now known to belong to the class following. (3) By gaseous or liquid aqueous emanations from ,large deep-seated masses of intrusive molten rock. These emanations, or mineral solutions, ascended through zones of connected openings in the earth's crust and dropped their load at points far above their source. Deposits formed in this manner were the primary source of nearly all, if not all, of the world's copper production.

Jan 10, 1923

By C Gunther

Ore deposits of commercial grade are local concentrations of great rarity when considered in relation to the area of unmineral¬ized land surfaces, and they must therefore be considered as the products of exceptional and complex conditions. The data collected from a great number of individual deposits are sufficient to permit certain broad generalizations in regard to the conditions favorable to ore deposition which even numerous exceptions do not invalidate. The broadest general relation of ore deposits is with intrusive rocks, and while there are notable exceptions, the great majority of ore deposits have a visible or closely inferred connection with intrusive rock masses. Conditions that permit the dissipation of the ore-bearing vehicles do not permit the concentration of metals in deposits; the prime factor to consider in this connection is that structural conditions must be such as tend to concentrate and not to dissi¬pate the ore-bearing solutions. The disadvantage of extrusive rocks is at once apparent; any metals the magma may have contained are dissipated at the surface and are lost; with the exception of tiny vugs and cracks in quickly cooled flows, no concentrations of metals are known in extrusive rocks, and the lack of confinement and quick cooling apparently do not permit extrusives to exert mineralizing effect upon the rocks with which they come in contact. The close mineralogical similarity between extrusives and intrusives, and the great difference in mineralizing power is a proof of the ease with which magmas part with their metallic content, and of the mobility of the ore-bearing vehicles in comparison with the parent magma.

Jan 1, 1932

By M. L. Brashears, R. G. Slayback

The host dolomite of the Pine Point lead-zinc ore is a prolific ground-water aquifer that occurs locally under watertable and artesian conditions. Mining schedules and severe climate require rapid and thorough dewatering of open pits. Pumping-test methods, common to ground-water supply studies, were applied to dewatering design for a model ore pit in 1968. Procedures for testing and design at other ore bodies were established and have been carried out successfully by mine personnel. At the inception of ground-water studies, parts of ore bodies were below prevailing ground-water levels by 35 to more than 150 ft. Movement of ground water through the coarsely recrystallized dolomite occurs largely through fractures and solution openings. Because the overburden deposits consist mainly of glacial till, it is estimated that the recharge to the aquifer is about 25% of the 13-in. annual precipitation. Natural groundwater flow is northeastward toward Great Slave Lake. Background data included extensive diamond drill hole logs and cores and static level data for a number of ore pits. An ore pit, known as N-42, that required 40 ft of dewatering was selected for the initial application of the pumping-test method. Production wells, cased with 14in. pipe, were drilled to a depth of 300 ft on the rim of the ore pit. A suitable pattern of observation wells was obtained by lining 21/8-in. diamond drill holes with perforated electrical conduit. A two-stage pumping test

Jan 1, 1973

By W. A. Tiller

The conventional techniques1 for determining the liquidus and solidus surfaces of an alloy system containing more than two components are extremely tedious to use and do not provide a complete picture of the equilibrium relations between solid and liquid alloys. These techniques are unable to yield "tie-line" information concerning solid and liquid phase equilibrium, a very important parameter in the solidification description of the liquid alloy and a very necessary parameter in the preparation of "zone-levelled" alloy crystals. The tie-line in a polycomponent system is analogous to the partition coefficient, k, in a binary system, it gives the composition of the solid, Cs, in equilibrium with a liquid of composition CL. That is, CS = kCL, where CL = [CO, c1,...Cn] denotes the concentrations of the n + 1 constituents, and k = [ko, kb ,...kon] denotes the gross partition coefficient for the elements between the two phases; thus, k is the tie-line in this system. To provide complete information concerning the two-phase equilibrium in a polycomponent system it is necessary to know both the liquidus surface and the gross partition coefficient. From these two the solidus surface is obtainable. The conventional techniques are unable to provide this information in other than a binary system so we must look elsewhere. In recent years considerable insight has been gained into the correct description of the liquid-solid transformation, 2,3 and controlled solidification experiments may now be designed to both facilitate and enhance equilibrium diagram studies. In the present paper consideration is given to two methods for obtaining the liquidus surface and the tie-lines in polycomponent systems. The methods to be described below deal with the solidification of an n + 1 constituent liquid alloy of initial composition [co, Co ,...Con], where the superscripts refer to the elements present and the Oth element is considered as the solvent in which the n solutes are dissolved. The general assumptions made in the treatment are the following: (i) the solid and the liquid at their interface are in equilibrium during the growth of the solid phase, (ii) there is no diffusion in the solid phase, and (iii) the liquid phase is completely mixed and is therefore homogeneous in concentration. METHOD I In this section a general experimental method will be described which, in principle, is capable of giving an exact description of the liquidus surface and tie-lines. Consider the unidirectional solidification of the liquid alloy specimens L cm in length (freezing either horizontally or vertically). Allow the sample to be frozen very slowly from one end, as indicated in Fig. 1, with complete mixing in the liquid, and then analyze the solid bar to determine its chemical constitution as a function of position, x, along the bar. Let Fig. 2 represent a possible distribution of the ith constituent along the bar. At the point x' the concentration of the ith constituent is C1/5(x'), and the average concentration of the rest of the bar between x' and L is given by C:(X' - L) where [ A(x) c1s(x)dx c1/s(x'-L) = f A(x) dx x * and A(X) is the cross-sectional area at x. In a similar manner. all the Cf(x' - L) may be determined. Thus, the gross artition coefficient k for liquid of composition [Cs(x - L),...Cs(X' - L)] is given by -ko= CUs')/Cos(x' - L)" k0 = csn{x')/cs(x'- L) During the freezing of a charge of length L, the liquid composition may vary over a wide segment of the phase diagram and the gross partition coefficient over this segment of the phase diagram may be determined from one, bar. Fig. 3 illustrates the magnitude of Cs(g)/C,' as a function of the fraction g of the bar which has Solidified.2 We can see that the concentration in the bar will vary over a range of about 15 wt pct for C,' = 10 wt pct and k0 = 0.5. It appears that 4 or 5 specimens would be adequate to study a simple binary eutectic phase diagram.

Jan 1, 1960

By Gordon C. Hicks

Prior to 1950 most fertilizer manufactured in the United States was produced in a nongranular form. In such form, the material caked when stored and was extremely dusty when applied in the field. About this time a wide interest developed in the fertilizer industry for the manufacture of a granular, high-analysis fertilizer of improved physical properties. Thus, TVA began work on fertilizer granulation about 1950 using both a pugmill (double-shaft paddle mixer) for a thick slurry of nitric phosphate and a continuous ammoniator-granulator drum for superphosphate-base mixed fertilizer. Granulation in these units was mainly by agglomeration. The liquid phase generated by the moisture and by the heat of reaction of ammonia with acidic materials, such as superphosphate and sulfuric or phosphoric acids, resulted in agglomeration of the solid ingredients. About 1956, TVA began studies of the use of a pan or disk granulator for production of ammonium nitrate or other fertilizers containing a large proportion of ammonium nitrate, such as 30-10-0 ammonium phosphate nitrate. This is the layering method of granulation. More recently, TVA has demonstrated pan granulation of urea from a highly concentrated solution and granulation of ammonium polyphosphate melts in a pugmill. The bulk of TVA studies throughout the years has related to use of the drum granulator. About 200 granulation plants in the United States have been licensed and built to use the TVA continuous ammoniator-granulator; it is estimated that more than half of the 20 million tons of mixed fertilizer used in the United States in 1974/1975 was produced in these plants. Some other granulation processes developed for use in the drum granulator include diammonium phosphate, monoammonium phosphate, urea- ammonium phosphate, ammoniated superphosphate, and most recently, NPK fertilizers by melt granulation using a pipe reactor.

Jan 1, 1977

STEPHEN TABER, Columbia, S. C. (communication to the Secretary?). -The fibrous salt crystals described by Dr. Branner are interesting, and I am glad that he has put this additional evidence on record. It confirms the results that I obtained in growing fibrous crystals in the laboratory. Much similar evidence of value to science in interpreting the laws of nature has doubtless been lost through failure to appreciate little things. Mr. Dresser points out that the boundary between chrysotile veins and massive serpentine is finely irregular 'when examined under the microscope. This fact I have observed in studying chrysotile veins and also, mode recently, in studying veins of fibrous calcite and fibrous gypsum. For the latter veins the statement holds true when the walls are of shale as well as when they are of the same material as the veins, but in no instance have I observed any evidence of replacement. The description of the vein walls given in my paper (pp. 1984 to 1985) was megascopic, not microscopic. The fact that chrysotile veins have sharply defined boundaries and are easily separated from the wall rock is evidenced by the small amount of waste adhering to the "crude asbestos" which has been shipped in such large quantities from some of the Canadian mines. Mr. Dresser has good ground for his statement that there seems to be no obvious reason why the term "mass fiber" should be restricted to anthophyllite. I have never examined the serpentine at the East Broughton mines; but in studying other serpentines under the microscope I have noted that much of the so-called "massive serpentine" is really finely fibrous (see pp. 1974 to 1975). The texture of such rock is, however, altogether different from that of mass-fiber anthophyllite, and I believe that the fibers have developed in a different way (see pp. 1981 and .1998). Mr. Graham raises certain objections on the ground that the laboratory production of fibrous crystals was limited to substances which go into solution with decrease in volume. Since my paper was written, however, I have succeeded in obtaining fibrous crystals of ammonium nitrate, a salt that dissolves with expansion in volume.

Jan 5, 1917

By Walter H. Bruckner, George B. Clark

SINCE the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained e1sewhere.l,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established concerning cavity liners: 1,2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as on the base diameter of the charge. Acute apex angles require thinner walls for optimum performance and more obtuse angles require thicker walls for the same base diameter. 2. Cones were more effective in forming a penetrating jet when the walls were tapered; i.e., the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical proper- ties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of Slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2. Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1947

Horace F. Lunt, York, Montana* :—Two years ago I visited the region described by Mr. Jennings and assisted in the examination of a somewhat similar group of deposits in the White Mesa sandstone on the Navajo Indian Reservation, 125 miles north of Flagstaff and 50 miles east of the Kaibab plateau. There, the Triassic red sandstone is less than 200 ft. thick, and is overlain by a stratum from 200 to 250 ft. thick of white sandstone, which gives the name of " White Mesa" to that locality. The white sandstone shows all phases of crossbedding in great complexity, and evidently marks a period of oscillation and subsidence of the water, or an elevation of the land, at the close of a geological epoch. The prevailing color is white or gray, but occasionally it is red. In structure, it is composed of well-worn grains of quartzsand, from which most of the cementing material has been leached out, leaving it soft and friable. Possibly the cement was ferruginous, as is indicated by occasional traces of red color. The copper-deposits consist of a replacement of the cement of one particular cross-bedded stratum of the sandstone by chrysocolla, having also at times various quantities of tenorite in grains or masses. Some specimens of the ore contain as much as 32 per cent. of copper. Generally the copper-deposits are a few hundred cubic feet in size, and no strict line of demarcation is shown between them and the surrounding sandstone, the bluish-green color of the chrysocolla gradually fading into the white of the sandstone. The ore is apparently associated with small vertical crevices or fissures. Some of the deposits show a distinct vein-structure, while others do not. The origin of the ore is not very clear. Undoubtedly the solutions, coursing through the crevices noted above, played a prominent part in its deposition, as possibly

Jan 1, 1904

By C. H. Li, R. J. Stokes, T. L. Johnston

Dislocation half-loops, artificially introduced by sprinkling with carborundum, were subjected to stress using three-point loading. The different stages of loop expansion and multiplication were then correlated with the macroscopic stress-deflection curve. Loop expansion started at approximately one-third of the "yield stress," defined here as the motivation stress. Above one-half of the "yield stress" simple multiplication commenced while about two-thirds of the yield stress gross multiplication developed short slip-line segments. These values were not affected by the age of surfaces exposed to both dry and wet air. Slip was not detected on unsprinkled crystals below two-thirds of the "yield stress." Thus the stress to activate intrinsic sources, defined here as the activation stress, was approximately twice the motivation stress. This relationship was independent of the strain rate used. It is concluded that lattice resistance takes the form of a viscous drag rather than a static type of force. THE importance of surface condition and environment as one of the more significant factors controlling the mechanical properties of ionic solids has recently received renewed attention.1-4 In some materials, notably the alkali halides, exposing freshly cleaved specimens to the atmosphere results in a progressive hardening and embrittlement of the crystals. This has been attributed to the surface layer becoming "aged," thereby restricting the motion of dislocations in such a way that pileup and eventually fracture results. It is necessary therefore in studying the mechanical properties of ionic crystals to inquire first into the density and distribution of dislocations in the normal cleaved surface and to understand the role these dislocations play in the onset of plastic flow. Knowledge of the effect of environment on this behavior will then assist in understanding the mechanism of embrittlement on aging. In the work reported here a method is described for studying the initiation of plastic flow from dislocation sources in the surface of magnesium oxide crystals. Preliminary results are described of the influence of surface age on this behavior. EXPERIMENTAL TECHNIQUES The magnesium oxide used in this investigation was obtained from the Norton Co. and had a nominal purity of 99.5.pct. Single-crystal specimens, having dimensions typically 1/4 by 1/8 in. cross section and 1 in. in length, were prepared by cleavage over (100) planes from the parent crystal. They were deformed under three-point loading with 3/4 in. spacing between the two end supports and a constant rate of deflection at the center of 0.001 in. per min. The maximum strain rate therefore was 1.5 X 10-5 sec-1. Reasons for choosing this particular form of loading will become apparent in a later section. In addition, a number of confirmatory type tests have been performed at higher loading rates where the maximum strain rate was increased to 1 x 10-3 sec -1. Following deformation the crystals were etched to reveal the dislocation distribution. In a previous paper5 we described a satisfactory etching solution consisting of 5 parts of saturated ammonium chloride, one part of sulfuric acid, and one part distilled water. Immersion of the crystals for 1/4 hr at room temperature developed reproducible conical etch pits at the points where dislocations emerged through the surface. It should be mentioned that dislocations freshly introduced by room temperature deformation gave sharply pointed etch pits which generally distinguished them from the almost flat-bottomed pits obtained on "grown-in" dislocations. The distinction is obvious in the photomicrograph included in Fig. 5(b). Annealing crystals at 1000°C for 12 hr on the other hand gave sharper etch pits on the grown-in dislocations and the distinction was no lower -possible; a similar observation has been reported for lithium fluoride. We have succeeded furthermore in chemically polishing magnesium-oxide crystals. Boiling in fresh 85 pct ortho-phosphoric acid for only 1 min resulted in a microscopically smooth surface which could again be etched to reexamine the dislocation distribution. This boiling time was sufficient to remove the surface damage introduced by cleavage (see next section). SURFACE DISLOCATION SOURCES There are a number of ways by which dislocations may be introduced into cleaved surfaces to act later

Jan 1, 1960

By B. S. Butler

STUDY of the ore deposits of Colorado has disclosed, in numerous places, sharp changes in both mineralogy and metal content of the primary or hypogene deposits with change in depth. A clear understanding of the meaning of these changes is requisite to form intelligent conclusions that can be applied in the exploration of such ore deposits. This paper is an attempt to set forth some of the geologic and chemical relations of minerals that bear on this problem. The effect of the differing electrode potentials of elements on the order of oxidation and on the order of displacement of one metal by another metal in supergene sulfide deposits has been studied for many years by several investigators. The results all agree rather closely with the original Schürmann series of replacability of metal sulfides, as Wells has shown.1 So far as the writers are aware there has been little attempt from the geologist's viewpoint to correlate the electrode potentials of the elements, other than those of the common metals, with the positions and mode of combination of the elements as found in ore deposits, and in particular in hypogene deposits. Wells' discusses electrochemical activity between solutions and certain ore minerals and mentions the possibility of its effect in precipitation reactions. The senior writer for a number of years has emphasized the importance of oxidation-reduction reactions as a factor in the formation of certain hypogene ore minerals, and as the electrode potentials are a measure of the relative oxidizing and reducing power of the elements and their ions, it seems possible that a study of them may offer some suggestions on certain problems. The data at present available for such a line of attack on oxidation-reduction reactions are too far from complete to offer much help, nevertheless the table of standard electrode potentials

Jan 1, 1929

By John T. Norton

In spite of the very general errlployment of nitride hardening, there is still considerable doubt as to the real nature of the mechanism involved. Experience has shown that the addition of small amounts of hardening elements to iron or steel results in a wide variety of desirable properties in a nitrided case. Perhaps the foremost of these elements is aluminum and in this investigation an attempt has been made to study the behavior of aluminum during the hardening process. It is believed that the establishment of a complete atomic picture of the metal at various stages of the process will indicate the relationships between the several kinds of atoms and their individual influences on the physical properties in a clear and direct fashion. A consideration of the problem suggests a surprising similarity between the mechanisms of nitride hardening and of age-hardening. It is now generally understood that age-hardening may take place by one of two distinct processes, the first involving the precipitation of a finely dispersed phase and the other being concerned with the modification of an existing phase. Following much the same line of reasoning, two theories of nitride hardening have been suggested. The first explanation, which has been generally discussed, particularly by Fry,' states in brief that the presence of aluminum causes the precipitation of aluminum nitride during nitriding and that this finely dispersed phase is the primary cause of hardening. The second explanation, which has not been published but which has been freely discussed by those interested in the problem, postulates the substitution of aluminum atoms for certain of the iron atoms in the several iron-nitrogen phases in the same manner that the substitutional iron-alurninurn solid solution is formed. The marked increase in hardness, as compared with the aluminum-free system, is attributed to the severe lattice distortion accompanying this replacement.

Jan 1, 1934

By E. L. Larison

DURING the early years of the present century a notable interest appeared in American industry in the matter of recovering and render-ing profitable byproducts of manufacturing operations. Among the byproducts of reduction of sulfide ores in many plants large amounts of sulfur dioxide gas were available. In certain instances the concentration of SO2 in the gases evolved was, or could be made, sufficient to make them suitable for manufacturing sulfuric acid. At the Anaconda Reduction works such a condition existed. Large tonnages of copper concentrate were being roasted and the roaster gases were available and suitable as a source of sulfuric acid. Earlier work on a large scale at Martinez, Calif., and in the Ducktown region, Tennessee, had shown the feasibility of manufacturing sulfuric acid from the SO2 contained in gases arising from the reduction of copper sulfide ores. In California and Tennessee the acid found a ready market in manufacture of fertilizers, while the situation regarding disposal of the sulfuric acid was quite different at Anaconda. No local use for acid existed, and a commodity of such low value could not stand freight charges to consuming centers. There was a very large accumulation of sand tailings from the gravity concentration mill below the plant at Anaconda. This material, made by the comparatively crude methods in use up to about 1915, contained about 13 lb. of copper per ton, largely as sulfide minerals. In 1912 serious research work toward recovery of this copper was instituted and after about two years of laboratory and pilot-plant development, a process for accomplishing it was perfected. This process involved roast-ing the sand tailings, leaching the roasted tailings with sulfuric acid, and throwing out the copper by passing the solutions over scrap iron. Under this plan each ton of sand required the introduction of about 70 lb. of 60° Be. sulfuric acid.

Jan 1, 1934

By E. L. Larison

DURING the early years of the present century a notable interest appeared in American industry in the matter of recovering and render-ing profitable byproducts of manufacturing operations. Among the byproducts of reduction of sulfide ores in many plants large amounts of sulfur dioxide gas were available. In certain instances the concentration of S02 in the gases evolved was, or could be made, sufficient to make them suitable for manufacturing sulfuric acid. At the Anaconda Reduction works such a condition existed. Large tonnages of copper concentrate were being roasted and the roaster gases were available and suitable as a source of sulfuric acid. Earlier work on a large scale at Martinez, Calif., and in the Ducktown region, Tennessee, had shown the feasibility of manufacturing sulfuric acid from the S02 contained in gases arising from the reduction of copper sulfide ores. In California and Tennessee the acid found a ready market in manufacture of fertilizers, while the situation regarding disposal of the sulfuric acid was quite different at Anaconda. No local use for acid existed, and a commodity of such low value could not stand freight charges to consuming centers. There was a very large accumulation of sand tailings from the gravity concentration mill below the plant at Anaconda. This material, made by the comparatively crude methods in use up to about 1915, contained about 13 lb. of copper per ton, largely as sulfide minerals. In 1912 serious research work toward recovery of this copper was instituted and after about two years of laboratory and pilot-plant development, a process for accomplishing it was perfected. This process involved roast-ing the sand tailings, leaching the roasted tailings with sulfuric acid, and throwing out the copper by passing the solutions over scrap iron. Under this plan each ton of sand required the introduction of about 70 lb. of 60° Be. sulfuric acid.

Jan 1, 1934

By S. J. Leach

The possible solution of some of the problems raised in H. L. Hartman's article "Determining Ventilation Requirements for Continuous Miners," which appeared in the March 1962 issue of MINING ENGINEERING, is offered by recent investigative work done at the Safety in Mines Research Establishment, Ministry of Power, Sheffield, England. Highlights of this research are outlined here. Accumulations and layers of methane form in a mine roadway because it is difficult to mix methane with air beneath it by turbulent diffusion. Such mixing involves work contrary to buoyancy forces. In specifying requirements for good ventilation it is not, therefore, sufficient to state that the airflow must be turbulent in the absence of methane. Fundamental work at SMRE on the behavior of methane roof layers has led to the formulation of rules for controlling methane roof layers which specify the ventilation velocity needed to ensure adequate mixing in terms of the rate of flow of methane into the layer (V = cu ft per min) and the airway width (D = ft). A "layering number" for methane and air has been defined by [U37/V/D] where U is the mean ventilation velocity in ft/min in the upper half of the airway. In a horizontal airway there is no mixing by turbulent diffusion for values of the layering number less than about 2, resulting in extensive roof layers. But with a layering number of 5, the layer is "brought under control"-i.e., a further increase in the layering number will shorten the length of the layer only slightly, and a small decrease in the layering number will cause only a small increase in the length of the layer. In a sloping roadway with uphill ventilation, higher values of the layering number are needed to achieve this "controlled" condition; the values range from about 5 at small slopes to about 8 at a slope of 1: 10. In downhill ventilation it is possible for layers to "back" against the ventilation, i.e., to flow uphill. The critical condition for preventing backing can also be expressed in terms of the layering number. Backing will be prevented if layering numbers are about 3 for small slopes and about 4.5 for large slopes; these values for downhill ventilation also give good control of the layer.

Jan 10, 1962

By Andrew Corry

GEOPHYSICAL investigations based on radioactivity have been applied to the earth's crust for the purpose of discovering bodies rich in radioactive substances, or for the location of solutions with high emanation or radioactive-salt content, or for the detection of oil, which, in virtue of colloidal properties, has strong powers of radioactive absorption. RADIOACTIVE SUBSTANCES Radioactive substances are distributed in all rocks, waters, and gases in the earth's crust in small quantities. Granites and similar acidic rocks are richest in uranium and thorium, two chief radioactive substances; yet the quantities present in such rocks are of the order 10-12g., this concentration being expressed in grams per gram of the whole substance per cubic centimeter. In granites the uranium yields, according to Haddock, 3 X 10-12 g. of radium per gram of rock. In basalts the uranium yields 1.19 X 10-12 g. per gram per cubic centimeter. Of thorium the granites yield -2 X 10-5 g. per gram of rock; the basalts, 0.77 X 10-5 g. per gram. Certain series of alkalis of low atomic weight, like potassium and rubidium, show weak radioactivity; this property has no significance so far for geological research. The uranium is esti-mated indirectly from the electrical properties of one of its derivatives as a -gas (emanation) into which it is transformed. The thorium is expressed directly, though it is measured as a derivative, thorium emana-tion. There is a measure for the gaseous radium emanation, the curie, which is that quantity of radium emanation, or radon, which stands in equilibrium with 1 g. of radium. The concentration of the emanation is the Mache unit corresponding to 3.64 X 10-10 curie per liter. When gases become permeated by alpha, beta, and gamma rays, plus and minus ions are produced in them by the decomposition of neutral gas molecules, and under the influence of an electrical field these ions are given opposite motions. The measurement of the alpha rays and the bisection thicknesses of the beta and gamma rays is a means of analyzing unknown radioactive substances. These rays accompany the disintegration of radioactive substances and arise from "spontaneous internal changes

Jan 1, 1929

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Henry A. Stiff

The classification and correlation of water analysis data presents many problems which can be solved by graphic methocis. The pattern system, a new type of graphic procedure described in this communication, is believed to have several advantages over older methods. Examples of the application, of the pattern system to the solution of problems encountered in petroleum production are given. INTRODUCTION Several graphic methods for presenting analytical water data have been developed and are now in use.1,2,3,4 It is believed, however, that a recently developed type of graph called the "pattern" offers several advantages over other methods. This system presents a better picture of the total salt concentration than is usual in such graphs. The effect of dilution or concentration has been reduced to a minimum, and at the same time distinction between various types of water has been improved. The system is extremely versatile, yet so simple it can be plotted on ordinary graph paper and adapted to almost any type of filing system. DISCUSSION The essential feature of the pattern system is the graph shown in Fig. 1. Horizontal lines extending right and left from a vertical line at zero form the graph. Positive ions are plotted to the left while negative ions are plotted to the right. The figure immediately beneath each ion gives the scale. Most oil field waters can be plotted on a scale where 100 milli-equivalents of sodium and chloride and 10 milliequivalents of each of the other ions are represented by one scale unit. For highly concentrated brines, 1,000 milliequivalents of sodium and chloride and 100 milliequivalents of each of the

Jan 1, 1951

By Henry A. Stiff

The classification and correlation of water analysis data presents many problems which can be solved by graphic methocis. The pattern system, a new type of graphic procedure described in this communication, is believed to have several advantages over older methods. Examples of the application, of the pattern system to the solution of problems encountered in petroleum production are given. INTRODUCTION Several graphic methods for presenting analytical water data have been developed and are now in use.1,2,3,4 It is believed, however, that a recently developed type of graph called the "pattern" offers several advantages over other methods. This system presents a better picture of the total salt concentration than is usual in such graphs. The effect of dilution or concentration has been reduced to a minimum, and at the same time distinction between various types of water has been improved. The system is extremely versatile, yet so simple it can be plotted on ordinary graph paper and adapted to almost any type of filing system. DISCUSSION The essential feature of the pattern system is the graph shown in Fig. 1. Horizontal lines extending right and left from a vertical line at zero form the graph. Positive ions are plotted to the left while negative ions are plotted to the right. The figure immediately beneath each ion gives the scale. Most oil field waters can be plotted on a scale where 100 milli-equivalents of sodium and chloride and 10 milliequivalents of each of the other ions are represented by one scale unit. For highly concentrated brines, 1,000 milliequivalents of sodium and chloride and 100 milliequivalents of each of the

Jan 1, 1951