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By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947

By C. S. Barrett, P. Coheur

AXnealing twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the re-crystallization texture,' and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (III), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3'4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture— this is true, for example, with the (113) [ZII] texture so commonly reported for brass—hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism. Materials and Methods The samples investigated were of secondary copper (melted in belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice have not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip I. cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a camera2 that traversed

Jan 1, 1947

By R. F. Evans, J. M. Avert

Much has been written of the glamour of magnesium from sea water, the Aladdin-like creation of a huge magnesium plant in the Nevada desert using cheap hydroelectric power from Boulder Dam; the marvels of the Hansgirg process for the electrothermal reduction of magnesium oxide by carbon, and the ferrosilicon process for producing magnesium from dolomite. This is the story of the production of magnesium by the electrolytic process, using steam-electric power supplied by a public utility, in a plant at Painesville, Ohio, 30 miles east of Cleveland on the shore of Lake Erie. The story is not without interest, since it involves several unique developments that provide the answer to a question frequently asked: How is it possible to produce magnesium metal economically at such a location as Painesville, Ohio? Basically, the answer lies in making use of facilities already in existence for the production of soda ash, which makes it possible to manufacture magnesium chloride, the principal raw material, cheaply enough to offset the high cost of electric power. To this is coupled the successful conversion of by-product chlorine into a product required for the war program. The source of magnesium for this opera- tion is the enormous surface deposit of high-grade dolomite in the region south of Toledo, within reasonable freight haul of Painesville. This same geological stratum underlies the Painesville plant, but unfortunately at a depth of about 3000 ft.— apparently too great a depth to permit underground mining to compete with the delivered cost of rock from surface quarries in other areas. The cost of dolomite obviously is an important factor, since the rock contains only some 12 per cent magnesium (20 per cent MgO) so that one dollar on the cost of stone means more than $8 in terms of its magnesium content, and more than that in terms of recoverable magnesium metal. Production of Magnesia from Dolomite In the summer of 1941, the Diamond Alkali Co. was well along with construction of a plant intended for the commercial production of refractory and other grades of magnesia from dolomite. The process to be used was designed to make maximum economic advantage of existing plant and operations by tying the production of magnesia in with the manufacture of soda ash in such a way as to make use of the lime [CaO)., value of calcined dolomite. The process finally adopted after a lengthy research and development program has much in common with the old Clerc-Nihoul process, but includes certain innovations found to be necessary or advantageous. Essentially, the process is based upon the following series of reactions:

Jan 1, 1949

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.' In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.' Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962

By Akio Suzuki, P. G. Wahlbeck

AS a part of a study of the vaporization of transition metal-chalcogen systems, the vaporization reactions for the Ti-Se system have been studied. In order to establish vaporization reactions it is important to determine the identity of vapor species in equilibrium with the condensed phases. In some cases, it is possible to deduce the identity of vapor species through observations of composition change of the condensed phase with which the vapor is in equilibrium. Determination of vapor species in equilibrium with condensed phases should precede vapor-pressure measurements and is necessary for proper thermodynamic analysis of vapor-pressure data. Bear and McTag-gart' reported that vacuum heating ot TiSea at 950°C produced a residue with a composition of 1.7 Se/Ti atomic ratio units. Analyses of condensed phases existing for the Ti-Se system have been performed by Bernusset,2"4 Gron-vold and Langmyhr,5 Hahn and Ness,' and Ehrlich.~ Results and conclusions of two types of experiments are described herein: 1) experiments where samples of known composition were vaporized followed by chemical analysis of residues and 2) experiments where the vapor species were identified by means of a mass spectrometer. Experimental Section. Sarnple Preparation. Samples of TiSe2 were prepared in a sealed, evacuated quartz ampule by heating to 1000°C stoichiometric amounts of selenium of 99.999+ pct purity obtained from the American Smelting and Refining Co. and titanium of 99.2 pct purity obtained from A. D. Mackay, Inc. After heating, the sample was ground and reheated to insure homogeneity. Samples containing less selenium than TiSez were prepared by mixing amounts of titanium powder and TiSez appropriate for the desired composition; the titanium and TiSez mixture was heated in the same manner as described for TiSe2. Analyses of titanium selenide samples contained in quartz crucibles were performed by gravimetric oxidation in oxygen at 800°C; the products of the oxidation were solid TiOz and gaseous Se02. The mass of the original sample and the mass of TiOn determined the Se/Ti atomic ratio. The sample of TiSen used in these experiments had a composition of 2.04 Se/Ti atomic ratio units. The compositions for all samples reported were analyzed by this method. Va/!orization Experiments. Samples of titanium selenides were vaporized in tungsten Knudsen crucibles. Some vaporization experiments were carried out in glass vacuum lines followed by chemical analyses of residues, and some vaporization experiments were performed with a Bendjx mass spectrometer as described previously.8

Jan 1, 1967

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

THE effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions The large number of alloys investigated made it impossible to study every one in the detail it may have merited Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold-working tends to disorder the structure, resulting in very marked lowering of conductivity The random state of atomic arrangement produces lower conductivity than the ordered state for the same composition 1 PREVIOUS WORK previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys The increase of resistivity due to severe working was less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21 7 per cent increase of resistance for an alloy containing 67 9 per cent Cu as severely worked Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens The resistance decreased again when the cold-worked crystals were subsequently annealed Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working The conductivity of 72-28

Jan 1, 1941

By C. S. Barrett, P. Coheur

ANNEALING twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the recrystallization texture,1 and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (111), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3,4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture this is true, for example, with the (113) [211] texture so commonly reported for brass-hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism . MATERIALS AND METHODS The samples investigated were of secondary copper (melted in Belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice has not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip 10 cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a cameral that traversed

Jan 1, 1946

By John L. Lamont, Walter Crafts

SELECTION of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of hardenability,1 as-quenched hardness,2,3 and tempered tensile strength.4 Ductility and toughness may also be estimated if the steel is completely hardened on quenching,5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In fine-grained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accompanied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to 4 in. in diameter. PROCEDURE The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1o30, 1040, 1340, 3310, 3316, 4320, 4330, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 9310, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.35. The bars were tempered as follows: ½ in., I in., and I 5/8 in., 2 hr; 2 ½ in., 3 hr; 4 in., 5 hr. All bars were air-cooled from the tempering tem-

Jan 1, 1947

By D. K. Crampton, H. I. Burghoff, J. T. Stacy

The effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail. Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys. Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions. The large number of alloys investigated made it impossible to study every one in the detail it may have merited. Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors. It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly. In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold--working tends to disorder the structure, resulting in very marked lowering of conductivity. The random state of atomic arrangement produces lower con- ductivity than the ordered state for the same composition.1 Previous Work Previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked. Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys. The increase of resistivity due to severe working w is less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher. In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21.7 per cent increase of resistance for an alloy contaiiiing 67.9 per cent Cu as severely worked. Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens. The resistance decreased again when the cold-worked crystals were subsequently annealed. Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working. The conductivity of 72-28

Jan 1, 1941

By J. P. Hirth, C. S. Hartley

A simple graphical technique is presented for rapidly determining the ratio of resolved shear stress on slip systems in single crystals to the applied stress (Schmid factor) for various simple states of stress. Master plots are presented which, when used in conjunction with an appropriate stereo-graphic projection, allow one to determine the Schmid factor for all slip systems in a crystal of given orientation. It is shown that one such plot suffices for simple tension or compression, flex-ural bending, and biaxial compression, while a combination of two different plots must be used for torsion and simple shear. STUDIES of the deformation behavior of single crystals are most valuable when the applied stresses are resolved onto the various slip systems of the crystal. A careful study of the available slip systems and proper selection of the state of stress used and the specimen orientation can then yield quantitative information about the probability of specific dislocation reactions, the strength of barriers to plastic flow, and the mechanisms of yielding and flow in general. It is the purpose of this work to analyze some common states of stress used in deformation studies and to present a simplified way of determining for these cases the ratio of the resolved shear stress on the slip systems to the applied stress (Schmid factor). I) CALCULATIONS We first define two orthogonal coordinate systems: one based on the specimen geometry (a right circular cylinder of radius, R, is considered here) and one based on the particular slip system of interest. The unit vectors and angles specifying the two coordinate systems and the relationship between them are listed in Table I. The relationships among the various angles and unit vectors are shown on a stereographic projection in Fig. 1. The transformation matrix between the (XI X2 X3) and (x'1 x'2 x'3) system is x1 x2 x3 X'1 a11 al2 a13 x'2 a21 a22 a23 x'9 a31 a32 a33 where in this case the direction cosines aij are given by a11 a12 a13 aij = a21 a22 a23 a31 a32 a33 sin 0 cos F cos 0 sin F cos 9 = -cos 0 cos F sin 0 sin F sin 6 [1] 0 -sin F cos (p In terms of Eq. [I.], the stresses sij, referred to the slip system, are determined from oij, referred to the specimen axes, by1,2

Jan 1, 1965

By R. F. Evans, J. M. Avery

MUCH has been written of the glamour of magnesium from sea water, the Aladdin-like creation of a huge magnesium plant in the Nevada desert using cheap hydroelectric power from Boulder Dam; the marvels of the Hansgirg process for the electrothermal reduction of magnesium oxide by carbon, and the ferrosilicon process for producing magnesium from dolomite. This is the story of the production of -magnesium by the electrolytic process, using steam-electric power supplied by a public utility, in a plant at Painesville, Ohio, 30 miles east of Cleveland on the shore 'of Lake Erie. The story is not without interest, since it involves several unique developments that provide the answer to a question frequently asked: How is it possible to produce magnesium metal economically at such a location as Painesville, Ohio? Basically, the answer lies in making use of facilities already in existence for the production of soda ash, which makes it possible to manufacture magnesium chloride, the principal raw material, cheaply enough to offset the high cost of electric power. To this is coupled the successful conversion of by-product chlorine into a product required for the war program. The source of magnesium for this operation is the enormous surface deposit of high-grade dolomite in the region south of Toledo, within reasonable freight haul of Painesville. This same geological stratum underlies the Painesville plant, but unfortunately at a depth of about 3000 ft. apparently too great a depth to permit underground mining to compete with the delivered cost of rock from surface quarries in other areas. The cost of dolomite obviously is an important factor, since the rock contains only some 12 per cent magnesium (20 per cent MgO) so that one dollar on the cost of stone means more than $8 in terms of its magnesium content, and more than that in terms of recoverable magnesium metal. PRODUCTION OF MAGNESIA FROM DOLOMITE In the summer of 1941, the Diamond Alkali Co. was well along with construction of a plant intended for the commercial production of refractory and other grades of magnesia from dolomite. The process to be used was designed to make maximum economic advantage of existing plant and operations by tying the production of magnesia in with the manufacture of soda ash in such a way as to make use of the lime (CaO) value of calcined dolomite. The process finally adopted after a lengthy research and development program has much in common with the old Clerc-Nihoul process, but includes certain innovations found to be necessary or

Jan 1, 1945

By Howard Thompson, H. N. Hall, Frank Nuss

Removal of bit cuttings is an important function of drilling muds. In an effort to obtain better understanding of the factors influencing the removal of cuttings, an extensive series of laboratory tests were made in which slip velocities of various sizes and shapes of particles were measured in muds of different physical properties. Empirical equations were then derived from these experimental data. These equations show that slip velocity is dependent on cutting size and shape, mud flow constants, and flow state of the mud. Applicability of these equations for field use is demonstrated by comparing computed slip velocities with slip velocities obtained from field tests. Drilling muds have many functions, but perhaps the most important is the removal of bit cuttings from the well. In a 10,000-ft well, the weight of rock which is drilled and must be carried to the surface is over 150 tons. In addition to this, the mud must remove any sloughings from the well bore. Failure of the mud to promptly remove either bit cuttings or sloughs from the well bore causes re-drilling and excessive wear on bit teeth, slows down drilling rate thereby increasing well costs, and greatly increases possibilities for stuck drill pipe when circulation is stopped for any length of time. Drilling muds lift bit cuttings to the surface by means of the upward velocity of the drilling mud in the annulus. Because a density difference exists between the rock being drilled and the drilling mud, there is a difference between mud velocity and the rate of bit cutting travel, called the net rise velocity. To evaluate the ability of any type of drilling mud in respect to lifting cuttings, some method must be known for predicting the rate of fall of cuttings through mud traveling upwards in the annulus. Equations for the rate of fall of particles through a true fluid have been satisfactorily determined by several authors. 1-6 Since drilling muds are not true fluids, but obey the laws of Bing-ham,7 it should not be expected that equations for rate of fall of cuttings in a true fluid would be applicable to plastic fluids such as drilling muds. Several authors have attempted to compute cutting slip velocities in muds using a viscosity value obtained with a Stormer viscosimeter; however, unsatisfactory results were obtained. Pigott8 took cognizance of the phenomenon of variation of viscosity with velocity in laminar Row, and calculated laminar slip velocities using a variable viscosity with Stokes law, and turbulent slip velocities using Rittingers law. Drilling muds obey the laws of plastic flow which involve factors not affect-

Jan 1, 1950

By D. K. Crampton, H. I. Burghoff, J. T. Stacy

The effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail. Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys. Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions. The large number of alloys investigated made it impossible to study every one in the detail it may have merited. Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors. It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly. In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold--working tends to disorder the structure, resulting in very marked lowering of conductivity. The random state of atomic arrangement produces lower con- ductivity than the ordered state for the same composition.1 Previous Work Previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked. Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys. The increase of resistivity due to severe working w is less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher. In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21.7 per cent increase of resistance for an alloy contaiiiing 67.9 per cent Cu as severely worked. Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens. The resistance decreased again when the cold-worked crystals were subsequently annealed. Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working. The conductivity of 72-28

Jan 1, 1941

By J. D. McClung

INTRODUCTION The ever increasing demand for coal sues that meet exacting specifications has made necessary the installation of thousands of dollars worth of crushing equipment by the coal industry. At one time the operator at- tempted to recover as much lump as possible but today he is confronted with the necessity of crushing to facilitate the mechanical cleaning process and to meet the demand for a variety of uniform sizes. As a matter of fact, about 65 percent of the coal mined in the United States today goes through preparation plants where it is crushed and cleaned. One becomes more aware of the importance of the art of comminution when it is realized that practically all of the operations in mining are involved in comminution in one way or another. Whether the coal is mined conventionally or by continuous miners it is separated from the solid by a breaking, ripping or milling action which essentially amounts to a comminution operation. Even degradation resulting from material handling from the mine working face to the preparation plant might in a broad sense be so classified, Then of course crushing is usually necessary in the plant before the coal is ready to be marketed. THEORY Despite the various comminution operations there is a lack of satisfac- tory information concerning the fundamentals of crushing and their relation to the variable factors associated with the operation. There are certain laws and theories on mechanical reduction, such as those of Rittinger, Kick and Bond that are helpful and useful. The difficulty in developing exact mathematical relationships for specific crusher applications is due to the many variable physical characteristics found in coal. Hardness, as measured by the Hardgrove grindability index, is one parameter that has been used for years to determine the resistance of coal to comminution. While the coal properties as measured by grindability are complex, recent work has shown that a high correlation exists between the grindability of some coals and their petrographic analysis. Early research on the hardness of petrographic entities from an Illinois coal2 demonstrated that durain was the hardest constituent followed by clarain, vitrain and very soft fusain. Other research demonstrated that, for different size fractions of the same coal, a wide variation in hardness commonly exists. For example, the fines in about half of 39 coals studied were softer than their corresponding coarse sues while most of the remaining coals were uniformly hard in all sizes. A few coals contained fines which were harder than their coarser constituents. These variations in hardness give insight into the heterogeneous nature of coal.

Jan 1, 1968

By Malcolm F. Hawkes, Robert F. Mehl

THE rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite.1.2 Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of G are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of -N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish. a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite, and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.' It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the "effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the martensite temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL PROPERTIES OF COBALT Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of the third shell. The next shell, which is the

Jan 1, 1947

By W. Crafts, J. L. Lamont

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By J. Rogers. K. L. Sutherland, E. E. Wark, I. W. Wark

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By J. L. Lamont, W. Crafts

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By J. L. Gillson

IN a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. GENERAL STATEMENT ON FLUORSPAR SITUATION Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in I901 for $5.81, in 1916 for $5.92. When the United States entered World War I, fluorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $I8.00 per ton. By 1935 the average price had fallen to $15.00, but in 194o with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, 'or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. [ ] Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be- again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1945

By G. W. Cullen

Niobium-tin has been prepared on insulating suhstrates hby simultaneous hydrogen reduction of gaseous niobium and tin halides. Stoichiometric material is greater than 98.8pct theoretical density, appears to he single-phase, and has a total impirity level less than 0.3 at. pct. Transition temperatures and lattice constants may he related to composition. Typical current densities in various fields and orientations are given. IT is known that Nb3Sn carries large current densities in high fields, 1 and exhibits an unusually high transition temperature2 and critical field.3 For these reasons high-field solenoids have been constructed of this material.4 Because of the emphasis on solenoid fabrication, much of the materials research has been directed toward development of wire geometries wherein the brittle Nb3Sn is supported by a more malleable metal or alloy. There are, however, basic studies and applications that can be carried out only on Nb3Sn supported by an insulator. Insulating substrates are desirable for a number of reasons: the substrate does not interact with applied or induced currents and fields; diffusion of metallic species into the de- posit is avoided, both during the preparation and during subsequent heat treatment; irradiated samples are not more active than the deposit itself. Unsupported Nb3Sn geometries may also be prepared by preferential chemical dissolution of the insulating substrate. This report describes the preparation and properties of Nb3Sn deposits on ceramic substrates. Experiments currently utilizing material prepared in the manner described in this report include the following: dependence of current-carrying properties on field strength and orientation 5,6 radiation damage,7,8 tunneling,9 thermal conductivity (substrate removed),1° microwave surface impedance," tube magnetization,6,12 resistivity as a function of temperature,13 and current density and transition temperature as a function of annealing.14 Possible practical applications include magnetic shielding, superconductor generators, and frictionless bearings. PREPARATION Methods for the deposition of elemental niobium and tin by hydrogen reduction of the gaseous metal halides have been known for some time,15,18 but only recently a procedure was developed in this laboratory17 for the codeposition of these two metals on a hotwire as the intermetallic compound, Nb3Sn. This method of simultaneous hydrogen reduction of the gaseous niobium and tin chlorides is used for the preparation of Nb3Sn On ceramic substrates. The procedure differs from that employed on a hot wire in that insulating substrates cannot conveniently be heated to temperatures greater than their surround-

Jan 1, 1964