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By Edward Schuster

As THE time allotted is short, we can present only a general idea of the oil laws in the Latin-American republics, as a supplement to Bulletin 206 of the Department of the Interior compiled under the direction of J. W, Thompson of the Bureau of Mines and entitled "Petroleum Laws of All America." We shall not discuss the European colonies in Latin-America nor the island republics. As to the countries discussed, we shall attempt to give the main features of such special petroleum legislation as has been adopted prior to the early part of this year; where no special petroleum" laws exist, we must look to the mining codes for light on the petroleum policy. As the laws and regulations for the extraction of the metals are often difficult of application to, and are lacking in many essentials for, the petroleum industry, it is best for persons or companies desiring to enter, on . a large scale, into the petroleum exploration and development of countries not having special petroleum legislation, to obtain a concession contract from the executive of the country under consideration, and to have the concession approved by the congress. If this concession, which would then be a special law, contains nothing contrary to the constitution of that country and does not infringe on vested rights of third parties, it should be reasonably safe. If in such country there is some doubt as to whether the petroleum subsoil is owned by the nation or the private surface owner, only public lands should be covered with the concession. Guatemala is the only republic in the group that discriminates directly against foreigners. Bolivia, Ecuador, Mexico and Venezuela require waivers of diplomatic protection.1 Colombia requires foreigners to agree to be bound by its alien law. , In addition,Mexico makes it unlawful for foreigners to acquire direct ownership of real estate, including mines, within a zone of 50 km. along the coasts and one of 100 km. along its land

Jan 7, 1922

By Frederic Benard

THE treatment of Balbach-Thum slimes at Copper Cliff by the Ontario Refining Co, is of interest because it differs considerably from methods usually employed for the recovery of fine gold from parting-plant slimes. Owing to the comparatively high percentages of palladium and platinum, wet methods are used to remove the greater proportion of these metals before electrolytic refining in the Wohlwill cells. THE PLANT The platinum-metals department, Wohlwill room, and gold-melting room extend along the north side of the silver refinery and are separated from the parting plant by a glass partition (Figs. 1 and 2). The platinum-metals department resembles a laboratory built on a large scale, with the various pieces of equipment laid out on terraces to facilitate handling. . Because of the corrosive nature of the solutions, chemical stoneware is used throughout. Elevation of acids is accomplished by means of Mariotte bottles. On the top level are three steam-jacketed stoneware kettles of 50-gal. capacity, also a packed tower. One kettle is used for digesting the slimes while the remaining kettles are used for precipitating the gold. The dissolver is equipped with a treated concrete hood, which is connected to the flue system. Gases are drawn off through the packed tower by means of a 6-in. stoneware exhaust fan. A 15 per cent solution of sodium carbonate is continually circulated through the tower. On the intermediate level are two suction filters, one for removing silver chloride and the other for the gold sand. The filter medium consists of an asbestos pad covered with a filter paper on which is a layer of twill. On the bottom level are two rectangular cementation tanks, 24 by 48 by 24 in. deep, and a suction filter used for removing the platinum-metal concentrates. The circulating pump for the packed tower is also here. Suction is provided by a vacuum pump having a capacity of 8 cu. ft. at 20-in. vacuum.

Jan 1, 1938

By Lewis A. Smith

Chromium is one of the new metals, but considerable research has been required to determine an approximate record of its production from 1827 until the present. Its use in the form of pure metal is not extensive; of the chromite mined, about one-half is required for making ferrochro-mium, about two-fifths goes directly into refractories and the remainder is absorbed chiefly by the chemical trades. The industries that demand chromite for such uses are mainly in countries that produce little chromite, while the important chromite-producing countries are not generally consumers. The international flow of chromite is therefore of interest, as well as the political and commercial control of resources of the metal. World Production The first mining of chromite is said to have occurred as early as 1820, at the Roros deposit in Norway, but the first well-established output came from the Reed mine, in Maryland, about 1827. Thereafter the United States led the world in chromite production until 1860, when Turkey took the lead. Russia in turn became the chief producer from 1897 to 1902, inclusive. From 1903 to 1909, New Caledonia held first place, but alternated with Southern Rhodesia from 1910 to 1917, inclusive. In 1918, 1919 and 1920-1921, the United States, India and New Caledonia led, respectively. In 1922 Southern Rhodesia assumed first place and has since continued to be the world's foremost producer by a large margin. Fig. 1 illustrates the production of the leading countries from 1890 to 1929, inclusive. Fig. 2 shows the world production of chromite from 1890 to 1929, inclusive, in long tons and Table 2 gives the production by countries for the same period. The total world production for the 103 years, 1827 to 1929, ipclusive, is estimated at about 7,100,000 long tons, distributed as shown in Table 1. World Trade in 1928 In reviewing the figures for the flow of chromite in 1928, it is evident that the six countries that produce most consume little chromite and

Jan 1, 1931

SANTA Rita del Cobre Grant, as the present Chino property was known in the early part of the nineteenth century, was the scene of the first copper-mining operations of consequence in the territory now included in the United States. As early as 1801, the mines afforded the principal supply of copper for coinage by the Mexican Government. According to an estimate made from old records by H. A. Thorne, now superintendent of mines for the Chino company, about 41,000,- 000 lb. of copper had been produced prior to 1845, when the exploitation of the native copper deposits of the Lake Superior district was started for the first time by white men. B. S. Butler, in Mineral Resources of the United States for 1913, estimated the production from Grant County, New Mexico, from 1845 to 1913, at 134,353,963 1b.-an amazingly precise figure, considering the character of the data that he must have used. As "Grant County" may be interpreted for practical purposes as the Santa Rita district, it seems fair to credit the Chino group with a production of 165,000,000 lb. of copper prior to the time when the modern operations commenced. Unlike Morenci, which, by the way, lies only about 80 miles westerly across the Arizona-New Mexico line, Chino offers no problem as to when its production might properly be classified as coming from a Porphyry Copper. The time is definitely fixed by the starting of the new mill at Hurley in October, 1911. The interval from 1903 to 1913 had witnessed little production of any kind; and prior to that time operations had been confined entirely to the mining of narrow veins or lenses of ore assaying 10 to 15 per cent copper or even more. Such orebodies frequently are encountered today, when the electric shovels, working in broad daylight, eat away rock that once was buried

Jan 1, 1933

By American Institute of Mining Engineers

David J. Mack (University of Wisconsin, Madison, Wise.)—Have the authors considered that the effects reported in their paper are readily explainable on the basis of equilibrium grain boundary segregation rather than ordering? It seems to the writer that all of their experiments and observations correlate well with known behavior associated with equilibrium grain boundary segregation. Although at first glance one would tend to dismiss such a possibility because of the similarity of the gold and copper atoms, their sizes differ by 12.8 pct which is in the range where segregation at grain boundaries would be expected. Then, too, the electrochemical differences between the copper, the Cu3Au, and the gold strongly suggest that a segregation mechanism is involved in the corrosion of the Cu-Au alloys. R. Bakish and W. D. Robertson (authors' reply)—The authors would like to thank Dr. Mack for his consideration of the problem of grain boundary segregation as an explanation of the observed phenomena. We had considered the problem in the following terms: Assuming a pure binary Cu-Au alloy and an ideal solid solution, the surface excess, T2= N25 — N2, of the second component (gold) may be expressed in the following way20 1 —exp (—da/kT) where 8 is the difference in surface tension of copper and gold, and a is the surface area per atom. In the present case, 6 is positive which implies that the component in excess at the boundary is gold. Since the only chemically active component in ferric chloride is copper, it does not appear that the segregation of gold is likely to increase the boundary activity. A small concentration of a third component could profoundly affect the situation. Analysis indicated only spectrographic traces of impurities, all of which are soluble in both copper and gold. Quenching experiments, reported in the paper, also tended to eliminate significant effects attributable to a third component.

Jan 1, 1958

By S. Andrew Kulin, L. Kaufman

A general treatment of the broadening of X-ray double-crystal spectrometer rocking curves due to distributions of tilts and strains has been carried out. The results of this treatment have been applied to the case where dislocations in a crystal give rise to both tilts and strains. On this basis it is found that the rocking-curve halfwidth due to imperfections in the crystal, ßC , increases with increasing Bragg angle, 8. These considerations predict linear relationships between & and tan2 , and ßCand tan 8, for Gaussian and Cauchy distributions of dislocations, respectively. The zero intercept of the ßC us 8 curve, which is a measure of the degree of imperfection of the crystal, is found to depend directly on the distribution rather than the number of dislocations. In addition, the slope-intercept ratio for the ßc - ? curve has been calculated for both the Gaussian and Cauchy distributions. Experimental determination of the - 8 curves for a series of copper single crystals prepared by the Bridgeman and Czochralski methods yields results in agreement with the calculated slope-intercept ratio for a Cauchy distribution of dislocations. CERTAIN X-ray techniques have been used to study the perfection of single crystals. Gay, Hirsch, and Kelly have considered the spreading of spots into arcs on Debye-Sherrer rings due to imperfections. The Double-Crystal Spectrometer has also been applied to this problem.2 The characteristics of Double-Crystal Spectrometer Rocking Curves have been described in the literature by various workers.2-4 By assuming a random spacing of dislocations which give rise to a Gaussian distribution of misorientations relative to some mean orientation in a crystal Gay, et al.,1 arrive at the conclu- sion that the most probable misorientation is given by where h is the spacing between dislocations, and 8 and are the relative misorientations of neighboring regions. If ßC is the halfwidth of the rocking curve (the width at one-half the peak intensity) due to dislocations in the crystal then5

Jan 1, 1960

By Wm. B. Price

The work of Leon Guillet concerning the effect of nickel on the structural properties of brass is checked. The best value for the coefficient of equivalence t, that is, the amount of zinc replaced by 1 per cent. of nickel, is shown to be-1.1 per cent. The best hot- and cold-working nickel silvers, varying in nickel content between the limits of 4 and 18 per cent., are tabulated and plotted diagrammatically. Also, some data are given showing a comparison between the physical properties of a hot- and cold-working low copper-nickel silver, and a commercial cold-working nickel silver containing approximately 8 per cent. more copper. THIS investigation of low copper-nickel silvers was undertaken to check the work of Leon Guillet on special brasses and to determine, more accurately, the effect of the addition of nickel on the microstructure of the binary alloys of copper and zinc. It was hoped that the results could be successfully applied to the practical production of low copper-nickel silvers. To explain the results of his investigations on special brasses, Leon Guillet evolved his conception of "fictitious compositions." He states,1 in his general conclusions, that on the introduction of a small amount of a third metal to a copper-zinc alloy, it enters into solid solution with the normal constituents up to saturation, but by so doing it brings the ternary alloy into a state microscopically equivalent to a binary copper-zinc alloy of fictitious composition, and physically more nearly like the latter than the brass containing copper-zinc in the ratio actually present. The physical properties of the ternary alloy, when compared to the same properties of an actual brass of the fictitious composition, are modified by the natural properties of the third element. Beyond the point of saturation, a special constituent appears and the above generalization no longer holds.

Jan 2, 1924

By Henry S. Rawdon

The relation between the course, or path, of the fracture of metals and alloys, produced in service or as a result of certain laboratory tests, and the crystalline units of which such materials are composed is of utmost importance. The fracture of normal material is, in general, intracrystalline, i.e., it consists of a break across the grains rather than of a separation between them. An interorystalline fracture indicates either that the metal is of very inferior quality or that the break occurred under very unusual conditions, e.g., at a very high temperature. The usual mechanical tests, when applied to metals of the type that breaks with an intercrystalline fracture, merely measure the coherence of adjacent grains for one another and reveal little as to the real properties of the metal itself. Even such a soft plastic substance as lead, under suitable conditions, may be rendered so weak and brittle that the metal can be easily crumbled into powder by the fingers although the constituent grains have lost none of the intrinsic properties of lead. Various erroneous explanations of this behavior of lead have appeared in the scientific literature, the change being described usually as an allotropic one. The importance, in an industrial sense, of a proper explanation of this type of the corrosion of lead justifies the description of the type of metal deterioration that follows. Corroded Lead Sheathing In Figs. 1 and 2 are shown two typical specimens of corroded lead sheathing selected from materials submitted to the Bureau of Standards for examination. Fig; 1 shows a section of the sheathing of an aerial cable; Fig. 2, that of the lead covering of a subterranean feeder-line of an electric light system. In this case the deterioration had proceeded to a much great'er extent than in the case shown in Fig. 1 so that certain portions of the metal could easily be crumbled into a coarse gray powder by the fingers. This was particularly true of those portions of the sheathing

Jan 1, 1921

By Geoffrey Gilbert

A study of specimens shows that the key to both oxidation and enrichment at Duck-town is the behavior of pyrrhotite, which is in part dissolved and in part replaced by marcasite. Enrichment takes place chiefly at the expense of marcasite. THE material that forms the basis of this paper was collected in the spring of 1922, during a ten-day visit to Ducktown by the writer in the company of Prof. L. C. Graton. The time available for the work was far too short to allow anything like a thorough study of the deposits, and structural and stratigraphic questions, though they have an important bearing on the origin of the primary ores, were necessarily left untouched. Attention was focussed on the zone of oxidation and enrichment; and by devoting most of our time to the upper levels, open pits, and old workings, and examining the deeper levels only thoroughly enough to obtain a fair idea of the nature of the primary sulfide ore, we were able to make a reasonably complete survey of the various orebodies. With this field work for a background, the writer later made a study, in the Harvard laboratories, of the specimens obtained during the visit. As some of the facts brought to light by this study appear to be new, it seems worth while to set forth the outstanding features and a proposed explanation of them. Much of the Ducktown material that is obviously of greatest significance, as regards oxidation and enrichment, is soft and crumbly. Notwithstanding the desirability of gaining from such material all possible information as to its mineral composition and textural relationships, but little has heretofore been learned regarding it; but, by suitable preparation of this material in connection with the present study, it has been possible to examine it under the microscope without any disturbance of its texture and about as satisfactorily as if it were hard, fresh ore. The information thus gained has contributed measurably to the results set forth in this paper.

Jan 3, 1924

By Murray F. Hawkins, W. J. Ainsworth

In all types of subsurface pressure gauges the extension which occurs in the pressure-sensitive element is a function of the difference between the external (well or calibration) pressure and the internal pressure within the gauge, rather than a function of the external pressure only. The internal pressure is near atmospheric and depends upon (a) the quantity of air sealed within the gauge at the time of calibration or measurement, (b) the quantity of moisture (liquid water), if any, sealed within the gauge, and (c) the temperature at which the calibration or well measurement is made. Part of this correction for the change of internal pressure with temperature is taken care of by the customary temperature coefficient of the gauge. However, part of it is not, and while this portion may be only a few psi, it is nevertheless predictable or preventable, and should be considered in precision measurements. ERROR NO. 1 If air is sealed in the gauge at the same temperature and pressure for both the calibration and the well measurements, the usual temperature correction will take care of any difference between calibration and well measurement temperatures. However, if air is sealed within the gauge at temperature T1 and pressure P1 at calibration but at temperature T2 and pressure P2 for a well measurement, because different amounts of air are sealed within the gauge in each case, the internal pressure at. or corrected to, calibration temperature Tr will he different by where all temperatures and pressures are absolute. The calibration temperature is used, and not the well measurement temperature, because the usual temperature correction reduces the well measurements to calibration temperature. The correction term as calculated by the above equation is separate from. and in addition to, the usual temperature correction. Example: T, = 540°R, sealing temperature at calibration P, = 14.7 psia, sealing pressure at calibration T2 = 460°R, sealing temperature at well P2 = 14.7 psia, sealing pressure at well Tr = 660°R, calibration temperature AP = 660 [14.7/460 — 14.7/540] = 3.1 psi While this error is small even under these somewhat maximal conditions, it nevertheless represents a practical situation which did occur, and which as a matter of fact gave rise to this note. Where AP is positive, as above, the correction is added to the measured pressure; where negative, subtracted from the measured pressure. This correction should also be considered in successive calibration runs where the gauge, for example, may be warm from a previous calibration at an elevated temperature. ERROR NO. 2 Where a small quantity of moisture (liquid water) is sealed within the gauge at atmospheric conditions, the increased vapor pressure of the water at higher well or calibration temperatures will cause an increase in internal pressure. This moisture will come presumably from condensation within the gauge following temperature changes, from moisture on the operator's hands, and from atmospheric moisture (rain, mist, fog, etc.). Calculation shows that approximately 0.2 cc of water (three to four drops) is sufficient to saturate the air within an Amerada RPG-3 Gauge at 160°F, at which temperature the vapor pressure of water is about 5 psia. As the vaporization occurs in a sealed volume, the increase in internal pressure will be in excess of this 5 psi. At higher temperatures the pressures will be higher; however more water will be required to saturate the air within the gauge. Some experimental work was carried out with an Amerada RPG-3 Gauge at 200°F fitted with a 1,000 psi element, both with a dry recording chamber and with a small amount of water added. The results directly proved the existence of the error due to the presence of moisture, and, it is felt, indirectly, due to the differences in sealing temperatures and pressures, as both effects may be ascribed simply to an increase in the moles of gas within the recording chamber. SUMMARY In precision measurements the error introduced by sealing the gauge during a well test at a different temperature and pressure from that of calibration may be corrected for by using the equation presented, or it may be prevented by taking care always to seal the gauge at near calibration conditions. The error introduced by sealing moisture in the gauge may be prevented by taking care to keep moisture out of the gauge, or by removing the moisture by either warming or evacuating the gauge. Both of these errors are independent of the range of pressure measurement and the type of gauge, and are in addition to the usual temperature correction. ACKNOWLEDGMENT Appreciation is expressed to W. B. Kendall, Geophysical Research Corp., Tulsa, Okla., who pointed out the error from differences in sealing temperatures during some winter work in Canada. ***

Jan 1, 1956

By Stanley L. Lopata, Eric B. Kula

SEVERAL methods are available for determining pole figures by X-ray means.' The earlier film methods have been replaced by techniques in which the intensities are measured by Geiger counters on an X-ray diffractometerZm7. These methods utilize either flat transmission or reflection samples,214°8 cylindrical specimens,3 or spherical specimens.7 A single transmission or reflection sample will not yield information over the complete pole figure. The cylindrical specimens suggested by Nortod and the spherical specimen of Jetter and Borie7 have the advantage of allowing the whole pole figure to be obtained without any corrections to the intensity for absorption, There is a lower limit to the size of sheet which can be conveniently studied, however, and sample preparation can be rather tedious. Probably the most common method today for determining the complete pole figure is that developed by Schulz. A flat reflection sample is used for determining the pole figure from the center out to about 70". Because of the geometry of the system used, little or no correction for absorption or irradiated volume is necessary.4'6 A separate transmission sample is used for the region near the edge of the pole figure. This procedure requires two separate samples, one of which must be a thin carefully-prepared transmission sample. Furthermore, since the reflection and transmission data are in different arbitrary intensity units, a region of overlap must be obtained, and the intensity data from one set of measurements converted to units of the other. These are serious disadvantages of this method, and they point out the need for a simplified procedure. Since the reflection technique can be used for planes whose normals lie up to about 70° from the sample surface normal, it is apparent that a complete pole figure can be obtained by reflection alone if sample surfaces are cut at oblique angles to the rolling plane Specifically, if a rolled sample is cut so that the normal to the surface formed lies equidistant (54" 44') from the rolling plane normal, rolling direction, and transverse direction, then complete information for one quadrant of the pole figure can be obtained by reflection from the surface. Fig. 1 shows this oblique surface, as well as the position of the pole of this surface in the pole figure. When a surface has been cut oblique to the rolling plane, the standard polar stereographic net is inconvenient to use, and it would be more desirable to have the center of the net coincide with the pole of the oblique plane. Fig. 2 shows such a net, where the center has been offset 54' 44' to correspond to a specimen cut as in Fig. 1. This net was in effect obtained by rotating a standard polar stereographic net 54" 44' with the help of a Wulff net. With the experimental setup used. a sample can be cut from plate of 1/2-in. thickness or br Gen- erally thinner sheet is under investigation, and a composite specimen must be used. A convenient procedure has been to bond together, using epoxy resin, sufficient sheets to form a cube. These are clamped in a vise, and when dry, the whole vise is rotated and a flat surface ground at the required angle. The sample is then mounted inside a larger steel ring using Koldmount, the backside ground flat and parallel to the approximate desired thickness. The sample is then polished and etched to remove any effects of cold working during grinding. With this method only one quadrant of the pole figure is obtained. Often pole figures show symmetry around the rolling and transverse directions, and any slight asymmetry is due to scatter. Should the pole figure not be symmetrical, four oblique surfaces, corresponding to the four quadrants of the pole figure, would have to be examined. In most cases there is symmetry at least around the rolling direction, which reduces to two the number of quadrants to be investigated. For many purposes all that is required is an average polefigure for the four quadrants. This canreadilybe obtained with composite specimens of sheet material, where sheets Corresponding to each of the four quadrants can be intermixed. The four quadrants can be obtained by considering sheet in the normal position, and by rotatiolls of 180" around the sheet normal, the rolling direction, and the transverse direction. If desired, the whole thickness of the sheet can be used, yielding an average of the surface and interior textures; or the surface material can be removed from each sheet, resulting in a pole figure for the center alone. Eugene S. Meieran of the Massachusetts Institute of Technology has independently developed the same method. His results, adapted to a pole figure goniometer with a specimen spiraler, will be described in another publication.

Jan 1, 1962

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By N. Standish

Heat transfer coefficients have been measured in beds of various packings irrigated with mercury and molten fusible alloy countercurrent to hot gases. The measured coefficients for both systems were found to increase with gas velocities and liquid rates. Correlations were determined which show this dependence and also indicate that heat transfer in these systems is influenced by the liquid flow characteristics and the thermal conductivity of the gas and the solid packings. A heat transfer model has beer2 proposed which explains the various features of the experimental results. On the basis of this study, which gives an insight into the heat exchange in the melting zone of the blast furnace, it was concluded that by comparison with the furnace stack heat transfer coefficients are about 1.5 times higher in the melting zone. EACH year large tonnages of metal are produced in operations which, in part, involve liquid metal irrigation of "packings" countercurrent to hot gases. The melting zone in blast furnaces and in cupolas is a good example of packings irrigated with a liquid melt countercurrent to gases. In all instances of this kind large amounts of heat are exchanged and it is desirable to have some knowledge of heat transfer phenomena involved in these systems. So far the most common method of analyzing furnace efficiencies, fuel requirements, and the general thermal state of the furnace has been through the use of heat balances. As heat balances are essentially statements of the first law of thermodynamics they give no real indication of the factors which govern heat transfer between phases in the various zones of blast furnaces. Hence, rational improvement in production efficiency and the development of theoretical models is only possible if the heat transfer characteristics are known at every stage of the process and related to the important variables involved. This has been generally recognized for some time but it was only recently that Kitaev et al.' have produced a comprehensive treatment of heat transfer in solid-gas countercurrent systems such as the blast furnace stack and the packed bed regenerator. Using their treatment it is now possible to predict the effect of particle size, thermal conductivity, bed porosity, and the flow rates of both the gas and the solid material on the heat transfer in the blast furnace stack. However, the stack of a blast furnace is only one part of an integral unit for which the heat transfer analysis cannot be complete without also considering the heat exchange in the melting zone. The complexity of heat transfer processes in this region of the furnace has so far escaped quantitative description. Yet, the melting zone accounts for a greater amount of heat exchange than all the other zones of the furnace put together. Moreover, if the reduction of oxides in the melting zone proceeds in part in the liquid state the importance of heat transfer on furnace productivity and on the metal and slag temperatures is obvious. THEORY Heat transfer for two-phase flow in packed beds is a complex problem involving a number of heat exchange paths for which interphase areas are not known with any degree of certainty. Analytical solution is, therefore, difficult. This difficulty is emphasized by noting that Rabinovich~ and Luck have only recently solved the steady-state heat transfer for simplified two-phase heat exchangers of known area. However, useful progress can be made for the system considered by making a not unreasonable assumption that the usual heat transfer considerations apply and restricting treatment to the steady state. For these conditions the rate of heat transfer dq in a height dz of a packed bed of unit area is: dq = UaATdz [I.] Integration of Eq. [I] then gives the total heat transferred: assuming both U, the overall heat transfer coefficient, and a, the interphase area, to be independent of bed height. Since a, in these systems, is unknown it is convenient to combine this term with U. The group U, then represents the overall heat transfer coefficient on a volumetric basis. If AT is linear with q, then for a bed of unit volume Eq. [Z] can be integrated to give: is the log mean of terminal temperature differences. From Eq. [3] U, can be readily calculated as q and {AT)im are experimentally obtained quantities, but a difficulty arises in interpreting its meaning. Two approaches are possible depending on whether the effect of packing in the transfer of heat is neglected or not. If the packing is thermally decoupled then the resistance concept gives the relationship: which states that the overall resistance is the sum of the gas phase and the liquid phase resistances (assuming areas are equal throughout). Because the resistance to heat transfer in liquid metals is negligible by comparison with that of the gas,4 Eq. [4] can be simplified, i.e.:

Jan 1, 1969

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.' It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By J. W. Snavely

THE high tension belt conveyor is introducing a new and tremendously expanded era of low cost bulk material handling. High tension belt conveyors are generally those installations involving very long centers, high lifts, or drops, in which the belts are stressed up to their maximum tension values, and further, where the belt construction provides tension capacity far beyond what is possible with conventional belt constructions. With these high tension installations, the magnitude of the forces involved demands careful refinement of accepted design practice in order to achieve optimum balance of all factors. No attempt will be made to evaluate the relative merits of belt conveyor haulage with other means of transportation. For present purposes, it is assumed this has already been done in favor of belt conveyor. Neither will any attempt be made to evaluate the various conveyor belt constructions now available or to balance the advantages of various types of mechanical equipment. It is also assumed that the basic haulage information on which the conveyor design is based is accurate and complete. A sustained maximum, uniform load on the belt at all times must be achieved through proper feed control and the use of adequate surge storage to level the peaks and valleys of any varying demand for the material being handled. General Belt Capacity Considerations The belt conveyor capacity tables published by various belting and conveyor equipment manufacturers vary to a considerable degree, and the ratings given are quite conservative. Of necessity, these published ratings are based on the handling of average materials under average conditions. In applying a high tension belt, all possible capacity from the belt must be obtained in order to hold its width to a minimum and thereby limit the initial cost. Two factors are involved, loading to maximum cross section area and traveling at a maximum practical speed. Belt Loading: Proper treatment of the loading of the belt will result in maximum cross section to the load, and published capacity ratings can be exceeded, sometimes by appreciable margins. On the 10-mile conveyor haul used in the construction of Shasta Dam, California, although the rated capacity of the belt line was 1100 tons per hr, at times the system handled peak loads of 1400 tons per hr, almost 25 pct better than the rated capacity. One of the large coal companies has been able to exceed rated capacity by as much as 50 pct. Loading conditions which must be controlled are: 1. Large lumps must be scalped off and rejected or the load must be primary crushed before being placed on the belt. 2. The material weight per cubic foot must be accurate, must be known for all the materials being handled, and must be known for the complete range of conditions of the individual material being handled. Long centers and high lifts magnify small differences into serious proportions. 3. Uniform feeding to the belt is most important. Various types of feeders are available, which can be used to place a constant predetermined volume of material on the belt, or, where an appreciable range of material weight exists, through electrical control actuated by current demand, to place a predetermined uniform tonnage on the belt. One long slope belt in a coal mine in Pennsylvania is being fed at three separate stations with the controls so arranged that whenever the maximum load is going onto the belt from the first station, the other two stations automatically cut out. Whenever the load from the first station drops back, the other two stations again automatically cut in. 4. Careful design of the chutes and skirts is necessary to get the load centered on the belt with a minimum of free margin along each edge. Some free margin at the edge of the belt is necessary to prevent spillage, but if the load can be kept accurately centered, this free margin area can be reduced, and more material can be carried on the belt. What can be accomplished in this respect will vary widely, depending on the nature of the material being hauled. The chute and skirt design must also protect the belt. 5. The design of chutes and skirts should also get the load traveling in the same direction and close to belt speed, so that the load comes to rest on the belt as quickly as possible. The design of the chutes and skirts is worthy of careful study, and after a system is put into operation it should be experimented with to get the best results. Belt Speed: High belt speeds should be used in high tension work. Obviously, high belt speeds enable haulage on a narrower belt, reducing initial cost. The major portion of belt wear takes place at the loading point and around the terminal pulleys. The

Jan 1, 1952

By R. D. Pehlke, P. D. Goodell, R. W. Dunlap

The rate of dissolution of steel bars in molten pig iron has been measured experimentally in the temperature range 2300° to 2650° F. The rate of solution is shown to be a .function of bath composition, temperature, and stirring. A kinetic model based on carbon diffusion in the liquid phase has been derived to fit the experimental results. THE rate of scrap melting has long been an important variable in steelmaking operations. With the advent of the oxygen steelmaking process and the accompanying shorter heat times, the rate of scrap melting has now become one of the rate-limiting factors in steel production. As observed in commercial practice, the solution rate is influenced by the compositions of liquid and solid, the temperature, agitation, and time. However, no definitive work has been done on the Fe-C system, and there is very little information in the literature regarding the relative effects of these variables in steelmaking systems. A number of questions have been raised in regard to scrap utilization in basic oxygen steelmaking operations. Consideration has been given to the optimum size and shape of scrap, and to the use of preheated scrap as a means for decreasing the pig-iron requirement in oxygen blowing. The determination of an optimum scrap practice for a specific installation depends to a large extent upon the economics of the scrap market and also upon the behavior of scrap in the vessel. The present research was undertaken as a preliminary study in evaluating the behavior of steel in a pig-iron bath under various conditions of temperature, composition, and agitation, as might be encountered in oxygen converter operations or in any steelmaking operation where scrap behavior is an important process variable. Related studies have been carried out on non-ferrous systems. The solution rate of solid aluminum in a molten A1-Si alloy has been studied.&apos; Furthermore, the increasing use of liquid metals has created considerable interest in studies related to dissolution of a solid in a liquid, or mass transfer taking place between a solid interface and a liquid metallic phase.2-10 In an effort to clarify the relative importance of factors influencing the dissolution of scrap in Fe-C alloys, this paper presents the results of a study of the rate of dissolution of a low-carbon steel cylinder in a molten Fe-C bath at various bath compositions, temperatures, and conditions of agitation. An attempt has been made to determine the mechanism of solution, and a model has been derived to fit the experimental results. The rate of heat transfer between the molten pig-iron bath and the solid-steel cylinder has also been studied. EXPERIMENTAL PROCEDURE A molten bath of pig iron (nominal composition 4.2 pct C, 0.5 pct Mn, 0.8 pct Si)* was held in a 200- *In view of the fact that the composition of the pig-iron bath was slowly changing with time because of steel dissolution and reaction with the surrounding atmosphere, intermittent samples of the liquid bath were taken throughout each experiment, Table 1. lb induction melting unit. The internal diameter of the furnace was 8-1/2 in. and the bath depth approximately 14 in. Cold-finished 1020 steel cylinders of 1/2-, 3/4-, 1-, 1-1/2-, and 2-in. diameters were cut into 1 -ft lengths for use as test specimens. One end of each bar was machined to fit a hand-driven, mechanical stirring device which rested on top of the furnace. This fixture permitted 7 to 8 in. of the bar to be immersed in the melt. The steel cylinders were cleaned to free the surface of grease and oxide. The rods, at ambient temperature, were immersed into the molten pig-iron bath. The melt temperatures studied in this investigation were 2300°, 2500°, and 2650°F. Different agitation conditions were achieved by operating with a) the power to the furnace, giving induction stirring; b) induction stirring plus mechanical stirring, using hand rotation with a chain and sprocket assembly at approximately 200 rpm; c) mechanical stirring alone with the power off; and d) the power off and no mechanical stirring resulting in minimum agitation, i.e., only that caused by natural convection currents in the bath. The samples were immersed in the melt for prescribed times ranging from 30 sec up to 6 min. Immersion times were measured with a stopwatch and temperature control of the melt was achieved by power adjustment following temperature measurement with an optical pyrometer. The measurements with the calibrated pyrometer were checked out to within less than 10°F with simultaneous thermocouple measurements. Following immersion, the bars were water-quenched and the diameters were measured with a micrometer at several positions on the reduced area, and by volumetric displacement. The dissolution rates calculated from the

Jan 1, 1965

By F. M. Lewis, J. F. Myers

W. I. Garms-—The authors state that when they added 11 tons of balls to the 45 pct volume ball load, the power needle did not budge. The question arises as to whether any increase in capacity accompanied the 11-ton addition. It is hardly conceivable that all of the balls making up the 11-ton addition were sterile. However, as the work done in the ball mill is not by kilo-watthours per se or balls per se but by kilowatthour-balls, it is possible that the kilowatthourballs in the mill before the 11-ton addition had a different amperage, voltage or robustage than those in the mill after the addition and that the overall outcome was that equal work was done before and after the addition. The authors can keep the efficiency that they got with the 45 pct volume 1-in. ball charge and get additional capacity by putting more kilowatthourballs to work in the form of the addition of 11 tons of 2-in. balls to the present ball charge, and subsequent makeup additions by weight of 20 pct 2-in. balls and 80 pct 1-in. balls. J. F. Myers (authors&apos; reply)-—Mr. Garms points his finger at the 11 tons of "sterile" balls added to the Tri-cone mill. A fact so interesting to us that we felt it should be reported. Clearly, ball slippage at the existing mill speed prevented any further transfer of power from the shell to the ball mass. We agree that the kilowatthourballs would increase, were we charging rough 2-in. balls as suggested by Mr. Garms. The assumption is, of course, that we would get a corresponding increase in work done. Our reported data (CIME meeting, Vancouver, 1946) shows a gain of work accomplished of 7.6 pct as we decreased the ball size from 2 in. to 11/2 in. and a further gain of work accomplished of 2.1 pct when we went from 11/2 in. to 1 in. The small ball results reported by H. R. Banks at Chapman Camp are also very convincing. In the case of 2-in. balls they would take the conventional ball path and start cascading. They would thus destroy the classifying pool over the "foot" of the

Jan 1, 1951

By J. F. Myers, F. M. Lewis

W. I. Garms-—The authors state that when they added 11 tons of balls to the 45 pct volume ball load, the power needle did not budge. The question arises as to whether any increase in capacity accompanied the 11-ton addition. It is hardly conceivable that all of the balls making up the 11-ton addition were sterile. However, as the work done in the ball mill is not by kilo-watthours per se or balls per se but by kilowatthour-balls, it is possible that the kilowatthourballs in the mill before the 11-ton addition had a different amperage, voltage or robustage than those in the mill after the addition and that the overall outcome was that equal work was done before and after the addition. The authors can keep the efficiency that they got with the 45 pct volume 1-in. ball charge and get additional capacity by putting more kilowatthourballs to work in the form of the addition of 11 tons of 2-in. balls to the present ball charge, and subsequent makeup additions by weight of 20 pct 2-in. balls and 80 pct 1-in. balls. J. F. Myers (authors&apos; reply)-—Mr. Garms points his finger at the 11 tons of "sterile" balls added to the Tri-cone mill. A fact so interesting to us that we felt it should be reported. Clearly, ball slippage at the existing mill speed prevented any further transfer of power from the shell to the ball mass. We agree that the kilowatthourballs would increase, were we charging rough 2-in. balls as suggested by Mr. Garms. The assumption is, of course, that we would get a corresponding increase in work done. Our reported data (CIME meeting, Vancouver, 1946) shows a gain of work accomplished of 7.6 pct as we decreased the ball size from 2 in. to 11/2 in. and a further gain of work accomplished of 2.1 pct when we went from 11/2 in. to 1 in. The small ball results reported by H. R. Banks at Chapman Camp are also very convincing. In the case of 2-in. balls they would take the conventional ball path and start cascading. They would thus destroy the classifying pool over the "foot" of the

Jan 1, 1951

By Jack White

W. I. Garms-—The authors state that when they added 11 tons of balls to the 45 pct volume ball load, the power needle did not budge. The question arises as to whether any increase in capacity accompanied the 11-ton addition. It is hardly conceivable that all of the balls making up the l l-ton addition were sterile. However, as the work done in the ball mill is not by kilo-watthours per se or balls per se but by kilowatthour-balls, it is possible that the kilowatthourballs in the mill before the ll-ton addition had a different amperage, voltage or robustage than those in the mill after the addition and that the overall outcome was that equal work was done before and after the addition. The authors can keep the efficiency that they got with the 45 pct volume 1-in. ball charge and get additional capacity by putting more kilowatthourballs to work in the form of the addition of 11 tons of 2-in. balls to the present ball charge, and subsequent makeup additions by weight of 20 pct 2-in. balls and 80 pct 1-in. balls. J. F. Myers (authors&apos; reply)-—Mr. Garms points his finger at the 11 tons of "sterile" balls added to the Tri-cone mill. A fact so interesting to us that we felt it should be reported. Clearly, ball slippage at the existing mill speed prevented any further transfer of power from the shell to the ball mass. We agree that the kilowatthourballs would increase, were we charging rough 2-in. balls as suggested by Mr. Garms. The assumption is, of course, that we would get a corresponding increase in work done. Our reported data (CIME meeting, Vancouver, 1946) shows a gain of work accomplished of 7.6 pct as we decreased the ball size from 2 in. to 1% in. and a further gain of work accomplished of 2.1 pct when we went from 1 % in. to 1 in. The small ball results reported by H. R. Banks at Chapman Camp are also very convincing. In the case of 2-in. balls they would take the conventional ball path and start cascading. They would thus destroy the classifying pool over the "foot" of the

Jan 1, 1951