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By Frank J. Markewicz, William Lodding

Greensand, greensand marl, and green earth are names given to sediments rich in the bluish green to greenish black mineral known as glauconite by the mineralogist. The word glauconite is from the Greek word glaukos, meaning bluish green. The term "greensand" as a rock name for a glauconite-bearing sediment is more appropriate than "greensand marl," a term that has been doggedly perpetuated in the literature. Because of its potash and phosphate content, greensand was dug and marketed as a fertilizer and soil conditioner for more than 100 years. The advent of prepared fertilizers with adjustable nutrient ratios led to the decline of green- sand for agricultural application. The material has since been recognized for use in water treatment. Unfortunately, in spite of large reserves and worldwide distribution, the mineral has not been utilized to any significant commercial extent because no major application has been found for a substance with its chemical composition and properties. This lack is probably due to a paucity of research on its potential commercial application. Extraction of potash received considerable attention during and just after World War I. Because of relatively high extraction costs and generally low potash content (up to 8%), glauconite lost its appeal as a source of this commodity. Historical Background Greensand was used as a fertilizer in New Jersey in the latter part of the 1700s. During the early 1800s its use became more common; applications of up to 100 tons per acre were sometimes made, although recommendations for agricultural use suggested 20 to 50 tons per acre (Tedrow, 1957). Many crops, especially the forage type, were said to improve with greensand application; however, because of slow release of potash, large quantities were required. Certain greensands that contain sulfur and sulfide minerals are harmful to plant growth, and these were classified as "poison," "burning," or "black marls." The availability of higher-grade potash salts from other mineral sources, and the manufacture of prepared fertilizers, displaced the agricultural use of green- sand during the later 1800s. During the mid-1800s the domestic greensand industry, centered in a small section of the eastern United States, grossed more than $500,000 per year. Toward the end of the century, annual production had dwindled to less than $100,000. By 1910 there were only six or eight greensand producers, grossing less than $5000 (Tyler, 1934). There was a small revival in the industry during World War I because of the curtailment of foreign potash, especially from Germany. During the later 1940s and early 1950s greensand was again recommended as a food nutrient for plants and farm crops. Agronomic studies discussed its potential as a soil additive that gradually releases potash and many trace- element nutrients essential for plant growth (Tedrow, 1957). Greensand was sold with the idea that it would condition soil and absorb and hold water while its base-exchange properties would release trace elements. For a short time glauconite was utilized in certain parts of New Jersey as a binding additive in the brick industry, and in the 1800s for making green glass (Cook, 1868). In the early 1900s the base-exchange property of glauconite was recognized for water treatment, and the mineral gained acceptance as a water softener. Mansfield ( 1922) does not mention base-exchange; however, the base ex-

Jan 1, 1975

By Paul Beck

IT is well known that the hardness of metallic single crystals, like that of polycrystalline metals, increases during deformation (hardening by cold-work). It is also known that, as a consequence of deformation, the metallic material acquires an evident thermodynamic instability, revealed, for example, by the fact that the increased hardness gradually decreases with time, especially at elevated temperatures (softening by annealing). The temperature at which the stabilizing process begins is different for various metals, and for any metal it depends on the amount of deformation. Such stabilization of deformed metals may proceed in two different ways: through recovery, and through recrystallization. The former process allows the unstable deformed metal body to approach stability gradually and without visible change in the grain structure; the latter process, like an allotropic transformation, yields directly the undeformed stable "phase" in the form of new undeformed crystals, which, starting out of a certain number of nuclei, grow into and' consume' the deformed hard material. The extent of stability attainable through recovery is limited, espe-cially if the deformation of the metal crystal or crystals involves not only the gliding along slip planes, but also the bending of the slip lamellae, or at any rate the bending of comparatively large parts of the crystal lattice. In such cases, for instance in bent single crystals or poly-crystalline metals subjected to any deformation, recovery will not as a rule be able to restore the "straight" undeformed lattice, and stability can be attained only by recrystallization; that is, by the consumption of the bent crystal lattice parts by new, undeformed crystals-a much more drastic process. It is evident that the part of the surplus free energy stored in deformed crystals, which is present in the form of the elastic energy of the bent lamellae, is in these instances not considerably involved

Jan 1, 1937

By C. D. Ramsden

DURING the war years of 1941 to 1945, maintenance of mine locomotives and other mine equipment took the form of rebuilding rather than of renewing. Pur¬chase of new parts became increasingly difficult and mine operators found it necessary to maintain equipment by sal¬vaging old parts. Mine-locomotive wheels, although not representing a high cost per pound of material, contain a con¬siderable amount of steel and without rebuilding would have to be scrapped long before even a moderate percentage of the steel in the wheel is actually consumed. Many mine operators have been re¬building locomotive wheels for several years with automatic open arc-welding equipment. In 1927, the Pittsburgh Coal Co. started such a program, using a single Westinghouse automatic welding head. Since that time, many refinements have been added, until in 1944 the setup was operating very efficiently. A desire to increase wheel life and to hold down rising costs led the company in 1944 to investigate the possibilities of the under¬flux arc-welding process for wheel rebuild¬ing, although at that time, little or no work had been done on multiple pass or "build-up" welding with the underflux arc. Work with this process had been confined largely to welding together flat plates in a "down hand" position. Possibilities for savings were intensified by the fact that the company has 300 locomotives in operation, using actively or as spares 1200 sets of wheels. During 1942 and 1943, about 500 sets of wheels were sent each year to the company's maintenance shop at Library, Pa., for rebuilding. Based on having 800 sets in service (many of the company's heavy locomotives have three- sets of trucks), the average life of a set of wheels was approximately 19 months. Anything that could be done to increase wheel life promised sizable annual savings. OPEN ARC WELDING With the open arc process, a set of wheels could be rebuilt for about 40 pct of the cost of new wheels. Underflux arc welding gave promise of greatly increased welding speeds, more homogeneous, dense deposits and the chance for use of a wider range in welding-wire compositions. Against this was ranged the higher cost of materials and the cost of developing the process from the theory to a practical reality. Since 1927, when a single open arc head was placed in operation, fixed welding procedures had been gradually developed, a positioner for handling a set of wheels was built, and a second head was placed in operation in order to weld two wheels simultaneously. The fixture, or posi¬tioner, which was built to position and turn the wheels under the two welding heads, included a motor drive, controlled by a rheostat, which rotated the wheels through a double set of speed reducers and a removable jaw coupling attached to one end of the axle of the wheel truck.

Jan 1, 1946

By John Wellington Finch

WHAT is an engineering opportunity? To the mining .engineer the natural assumption is that the first requisite 'is a mineral deposit, but, of course, it is not so simple as that. There are at various points on the earth really very great mineral deposits which, on account of geographic location, backwardness of the country, or hostility of its natives, are now, and for a long time to come will be, quite valueless. The mining engineer, and for that matter the civil engineer, is more dependent upon the decisions of capital than upon any other factor in his profession. Ordinarily it is to be assumed that money will go to any place where it is clear that an adequate return upon its investment can be secured, but for many years it has not been safe to depend upon this. ' As already stated, there are many places where local conditions are such that mining is not safe to engage in and there are still other places in which conditions have been so aggravated by the Great War and by the social unrest which has upset the Asiatic region that capital is naturally most reluctant to venture, even when engineering data makes the undertaking appear attractive. It will be evident, I. believe, that there are many factors vital to the success of a mining enterprise in some of the remote countries which we do not have to consider in the United States and which do not, in fact, exist here.

Jan 1, 1924

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By C. L. HUSTON

MY ANCESTRAL connection with the manufacture of boiler plate runs back through four generations, and my personal acquaintance with the practice reaches back to the time, in my ,boy- .hood days, when iron plates' were made in a mill operated entirely by water power. -The mill originally was driven by an old-fashioned "'breast" water wheel 20 ft. in diameter and with a20-ft. face, geared direct to the roll train. When the mill slowed up and there was danger of its stalling, the men would jump upon the rim and help the wheel around with their weight, to prevent a "sticker." Later, as large plates were called for, a flywheel was set out of line so that it could' be speeded up by gears from the water wheel and connected back again,. by reducing- gears, to the roll train. The flywheel, with its cast-iron rim and wooden spokes, made 90 r.p.m. and the roll train 45 r.p.m. In 1870, our company installed our first steam-driven plate mill two-high rolls, 84 in. long. In these early mills the hot metal was manipulated by hand.

Jan 1, 1920

By H. W. Morse

The experimental work on the oxidized copper ore at the New Cornelia mine at Ajo, Ariz., ended on Jan. 12, 1916. On that date final decision was made on the general nature of the process to be used in the 5,000-ton leaching plant, and on many of the details, as far as experience on a 40-ton scale could decide them. With the approval of the Board of Directors and the General Manager, John C. Greenway, we have compiled what seem to be the most interesting data on the results obtained during the experimental period. The most important part of the data resulted from the operation of a 1-ton and a 40-ton plant at Ajo. Experimental work on Cornelia oxidized ore dates back to April, 1912, and has been going on nearly continuously since that time. A good many variations from the original idea have been tried, but the process finally decided upon is in principle and in all of its details a simple one. The history of the leaching work on this ore has been brought down to about a year ago in papers presented to this Institute by Stuart Croasdalel and Dr. L. D. Ricketts.2 The present paper will, therefore, deal principally with the results obtained during the last year of the work. Preliminary Tests by Mb. Croasdale Preliminary tests were begun by Stuart Croasdale in July, 1912. A number of important points were definitely decided by his work. Among these were: 1. New Cornelia oxidized ore, not very finely crushed (to about 2-to 3-mesh) showed good extraction with 5 per cent. sulphuric acid. It appeared that better than 80 per cent. extraction could be expected. 2. The consumption of acid for this extraction was not prohibitive. It was apparently 3.5 to 4 1b. gross per pound of copper recovered.

Jan 1, 1917

By Glenn A. Marsh, George Bernard

It is often assumed that aerated oil field brines which are to be injected underground contain dissolved oxygen in amounts which will cause appreciable corrosion. Through the use of a new portable dissolved oxygen meter, accurate determinations were made at three brine conditioning plants. At two older plants, dissolved oxygen concentration in the final treated brine was found to he almost zero In spite of aeration during the conditioning process. At a new plant, dissolved oxygen was initially present but disappeared soon after the brine was "inoculated" with oxygen-free brine from one of the other plants. Corrosion tests at the two older plants have substantiated predictions that the brines would lint be corrosive. These results show that mechanical deaeration may not always be required in brine treating plants. INTRODUCTION The present work was undertaken to add to our knowledge of aeration and deaeration of oil field brines in brine conditioning plants. It is commonly assumed that brines which are exposed to the air soon become more or less saturated with dissolved oxygen. Since oxygen-containing brines are known to be corrosive, precautions are often taken to keep air out of brine through the use of closed systems or mechanical deaeration. The study of oxygen in brine has been seriously hampered in the past because of the lack of a suitable analytical tool. The standard Winkler method for the determination of dis-solved oxygen is satisfactory for use in fresh water, but not in many oil field brines. Corrections have to be made for a number of reducing substances such as ferrous iron and hydrogen sulfide which are commonly present in natural brines. Very often the correction factors are much greater in magnitude than the amounts of oxygen which are to be determined, and consequently erroneous results are obtained. Also. erratic Winkler data are obtained when appreciable concentrations of calcium and magnesium salts are present. The first step in carrying out a systematic study involved designing a portable dissolved oxygen apparatus which would operate in natural brines. Subsequently, this apparatus was used in three brine conditioning plants. Dissolved oxygen data obtained here, and certain corrosion rate data, illustrate the interesting behavior of oxygen in these oil field brines. APPARATUS A portable dissolved oxygen meter described in detail elsewhere,' was developed specifically for use with oil field brines. It is a polarographic apparatus employing a small rotating platinum electrode (cathode) and calomel reference electrode (anode). A potential of 0.7 volts is applied across the electrodes while they are immersed in the brine to be tested. 4References given at end of paper.

Jan 1, 1952

By Joseph Daniels

(San Francisco Meeting, October, 1911.) I. THE FRITZ ENGINEERING LABORATORY. TEE Fritz Engineering Laboratory was built under the direction of John Fritz, and presented by him to the University. A view of the building, looking east, is shown in Fig. 1. . The building was started in 1909, and completed in 1910, although all of the equipment was not placed until later. Mr. Fritz gave his personal attention to the details of construction and equipment, and it was his custom to drive over every day to the University from his home in Bethlehem, and spend some hours watching the work, offering suggestions, making changes, and planning new work. The result is a building and an equipment which embody his practical ideas. The laboratory structure is of the steel mill-building type, of light-colored brick, 91 by 114 ft., of which a section is shown in Fig. 2 and the floor-plan in Fig. 3. The steel frame carries the roof and traveling crane-way. Ample light has been provided by numerous windows in the side and end walls, in the clerestory, and by a skylight, 84 ft. long and 9 ft. wide, in the north roof. The main aisle of the building is 49 ft. 2 in. between centers of crane-columns, and has a clear height of 40 ft. The remainder of the width is taken up by two side aisles, 18 ft. high. The laboratory consists of four sections: (1) A general testing-section, containing the testing-machinery, a small machine shop, and an office; (2) a cement-testing room; (3) a room for making and storing concrete test-specimens; (4) a hydraulic section.

Feb 1, 1912

By Persifor Frazer

At a time when all those interested in the iron trade are carefully scanning the horizon for new sources of the raw material, a few words concerning a field, which though not new, has not been hitherto fruitful of statistical information, may be deemed appropriate at this meeting. The district alluded to is the belt of the Middle James River, or in other words, that portion of the ferriferous belts of Virginia lying between Josua Falls and the little settlement of Norwood, in the counties of Amherst and Nelson, and on the left bank of the James River. This region shows unmistakable signs of developing a very considerable market for iron ores and for iron in the future, as well as a tempting appearance of possible productiveness in the former. It, is extremely hazardous to deal in generalizations as to the productiveness or non-productiveness of these measures without a more thorough development than has yet been attained. It is true that they probably constitute an horizon whence comes a part of the marvellous mineral wealth of the northern peninsula of Michigan. But

Jan 1, 1883

Jan 1, 1902

By AIME AIME

THE autumn is the time that nearly all the special groups within the broad field of the Institute's activitives chose for their own special meetings. The big annual meeting in New York in February has its own special advantages, but to realize them involves sacrificing others. A meeting of a smaller group with the subjects brought up for discussion much more closely limited to a single field of interest has some advantages that a big general meeting cannot possibly have. And so the custom has gradually developed of having these smaller meetings in the autumn, at con¬venient places, so the men will not have to travel too far from the job to be present. Sometimes the meetings have for their field of interest a single phase of mineral technology, and are called divisional, and at other times they cover a diversity of topics that are locally important in that geographical area, and are then called regional meetings. Of the five meetings to be held this fall, four are divisional and one regional. Two of the divisional meetings are to be held in the same place at the same time, but with programs so arranged that they do not conflict.

Jan 1, 1930

By K. Huessener

INTRODUCTION THIS paper attempts a survey of the principles involved in the com¬bustion of blast-furnace gas in boilers and stoves. I do not expect to be able to give much information which is actually new, since the laws and methods of calculation pertaining to this problem are contained in a number of handbooks; but, so far as I am aware, they have nowhere been treated exclusively with reference to this one problem of gas economy. The road which I follow is less that of strictly scientific research than that of the practical engineer, faced by operation problems which require a. quick solution by easily accessible means without a prolonged search in scientific handbooks. For this purpose I give a number of tables and diagrams, as well as the results of many years' practical working experience as combustion engineer, which I trust will prove useful to my readers. HISTORICAL Considering the tremendous efforts made during the last 15 years to increase the efficiency of all kinds of power plants, it is highly surprising that until a comparatively very recent period, progress in the economical combustion of blast-furnace gas has been so slow. The explanation generally put forth, that fuel has been so cheap that it was hardly worth while to bother about this economy, will not hold good, for the greatest trouble was taken to improve the combustion of coal and to reduce the consumption of steam. The most plausible explanation appears to be the general impression, held as an accepted fact, that gas, especially hot, uncleaned, blast-furnace gas, was not a good boiler fuel. Many managers of high repute had tried unsuccessfully to improve the conditions of its use, and the dictum went forth that efficiencies of over 60 per cent., particularly with high loads, were impossible. This was the situation not only in the United States, with very cheap fuel, but also in Europe, where fuel prices are twice and three times as high.

Jan 2, 1916

By T. A. Wright

THE SAMPLING of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or "metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can he readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also. As a matter of fact, we may expect that improved refining processes will make possible the partial recovery of lead and tin which are now lost.

Jan 1, 1928

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By K. E. Nelson

The effect of thorium and zinc variations on the strength and 100-hr creep characteristics of Mg-Th-Zn-Zr alloys was investigated. Optimum resistance to creep at 650° and 700°F are attainable within a certain range of thorium and zinc contents. This range does not conform to that which develops maximum tensile properties. RAPID advances have been made during the last few years in the development of magnesium alloys for elevated temperature applications demanding high resistance to creep. The beneficial effect of rare-earth metals on the creep resistance of magnesium alloys has been emphasized by a number of publications1-13 and such alloys are now in commercial production. The use of thorium as an alloying ingredient in magnesium was mentioned by McDonald and also in two Alien Property Custodian patent applications.10,17 The initial observation of Sauerwald that thorium contributes still higher creep resistance to magnesium than is attainable with rare-earth metals has recently been substantiated.'" " In fact, it has been demonstrated that the useful temperature range of magnesium alloys is appreciably extended by the use of thorium. In all cases, it was observed that zirconium must be included in the alloys in order to render them fine grained and more readily castable. Several recent publications:2-27 indicate that a still further improvement in creep resistance and a further extension of the useful temperature range can be realized by the addition of zinc to alloys. The primary purpose of this paper is to present the results of a comprehensive study of the effect of zinc on the strength and creep characteristics of Mg-Th-Zr alloys. Compositions covering the range of thorium content from M to 6 pct and zinc content from 0 to 5 pct have been investigated. The creep characteristics at 650" and 700°F reported in this paper are based on results of tests of 100-hr duration. It is appreciated that creep tests of 100-hr duration might not yield adequate data for design purposes for parts with much longer expected life. However, for the purposes of the present discussion, it is felt that the combination of stresses and temperatures used in the 100-hr creep tests have yielded a clear representation of the compositional variation of creep resistance at the temperatures investigated. Creep tests of 1000-hr duration are now in progress on a few of the most promising alloys. Preparation and Testing of Alloys The alloys studied in this intensive investigation were prepared in 25 lb capacity mild steel crucibles. The thorium, zinc, and zirconium were alloyed and poured as described in earlier publications The thorium was introduced into the melt in the form of a Mg-Th hardener," the zinc added in the metallic form, and the zirconium alloyed in the form of the commercial hardener containing magnesium and 30 to 50 pct Zr.10, 26 Fluxing practices for melting and refining were the same as for magnesium-rare-earth metal-zirconium alloys. The melts were sampled for analytical determinations and poured into separately cast 1/2 in. diameter standard tensile bars. The test bars were given a precipitation treatment of 16 hr at 600°F in laboratory furnaces. It has been shown by other tests that a high temperature solution treatment followed by an aging treatment is unnecessary for the development of optimum properties in Mg-Th-Zn-Zr alloys. The selection of 600°F as the aging temperature was based on an attempt to achieve metallurgical stability without coalescence of the undissolved phases and the attendant loss in strength. The thorium, zinc, and zirconium contents of each melt were determined chemically. The zirconium contents are reported in two parts, "soluble" and "insoluble," referring, respectively, to the portions present in the alloy which are soluble and insoluble in dilute HCl acid. Distinction is being made between these two components of the zirconium content in the alloys because it has been found that only that portion of the zirconium content which is soluble in dilute inorganic acids affects the structure and properties of the alloys. The usual impurities consisting of copper, iron, manganese, and nickel were determined spectroscopically. The analysis for each melt is listed in Table I. A description of the methods of tension and creep testing has been detailed in earlier papers. The tests were performed with the cast skin re-

Jan 1, 1954

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß' and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß' varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

By W. A. Tiller, W. C. Johnston

A high-temperature electromagnetic stirrer is described in which heating and stirring are accomplished by independently controlled power sources. The appavatus is suitable lor use at temperatures up to 1700°C in a variety of ambient atmospheres. Some typical examples of the homogenizatimz capabilities of the system are given. THERE are few processes in solidification that are not markedly affected by motion in the melt during freezing. In many instances, the mechanisms are diffusion-controlled, and the transport in the melt may be greatly accelerated by deliberately stirring the melt. In zone-refining, stirring1 assists the removal of rejected impurities from the interface, so the process proceeds at a faster rate. The transition from a planar to a cellular interface is caused by constitutional undercooling in the melt ahead of the interface: and stirring delays its onset. Stirring is valuable for homogenization of melts: and chemical reaction with sluggish kinetics may be accelerated. Finally, it has been observed that grain refinement is related to motion in the melt. Fine grain castings are usually produced by the addition of catalysts to the -melt,' catalysts which are thought to act simply as hetereogeneous nucleation centers. Even here motion is important. Richards and Rostoker 5 applied ultrasonic vibration to a solidifying A1-Cu alloy which had been innoculated with a catalyst and found that the grain diameter fell linearly with the amplitude, the peak acceleration and the power input to the melt from the transducer. Finally, mechanical and electrical stirring alone have been used to generate a fine-grained structure.6,7 Johnston ef a1.' have carried out a series of systematic investigations of grain refinement by electromagnetic stirring in a number of low melting point alloys. They found, for example, that the number of grains per unit volume in Pb-Sn alloys could be increased several orders of magnitude by stirring an undercooled melt at the moment of recalescence. In general, a relation AT .H = constant prevailed for a given grain size, where AT was the undercooling of the melt and H the field strength. In more recent work, deliberate homogeneous nucleation of slightly undercooled melts established that the mechanism of refinement must be one involving crystal fragmentation and subsequent multiplication, rather than a "shower" of nuclei effect.9 It is the purpose of this note to describe a stirring device suitable for use up to 1700°C. At low temperatures mechanical stirring and direct-current methods are feasible, but at high temperatures the problem of a protective atmosphere and of electrode corrosion rules out such procedures. The most convenient method for high temperatures is to use externally generated ac fields for both stirring and heating. With rf induction heating alone, considerable stirring and agitation can be achieved, but in general the penetration of field into the melt is small, and the stirring cannot be controlled independently of the heating. In the present experiments, separate power sources of different frequencies for heating and for stirring were used. A susceptor design was chosen so that the 450 kc rf heating field was completely absorbed in the susceptor. The stirring frequency, 400 cps, hereafter called the af field, was chosen so that a high penetration of the melt proper was achieved. EXPERIMENTAL APPARATUS The apparatus, Fig. 1, consists of a quartz tube and end plates, surrounded by an rf induction coil and six equally spaced af stirring coils, four of which are shown in full and a fifth in section. Each af stirring coil is a transformer of which the secondary is a single-turn water-cooled copper loop and the primary is composed of two 10 amp-117 v Variac cores as shown. These cores are cooled by forced air, as each of the six pairs will carry maximum currents of 15 amp for short periods. Each set of Variac windings are connected in series, but opposite sets are connected in parallel with a three-phase 400 cps 400-v source. By properly phasing the coils in this way, a rotating field is produced. Capacitors C1, C2, and C3 in Fig. 2 are used to match this inductive load to the generator. Fig. 3 shows a cutaway view of the quartz tube. The sample (1 in. diam by 1 in. high) is placed in a tapered alumina crucible. An axial W-26 pct Re thermocouple, enclosed by a protection tube, is provided. The cruci-

Jan 1, 1968

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By Benjamin Miller

FROM earliest recorded times, limestone has been employed in the industrial life of peoples of all sections of the world where it exists. It is widely distributed and therefore has been available in almost every country and has been employed for a variety of purposes. Its earliest use was for buildings, since it is more easily quarried and dressed than most other kinds of rocks and so could be utilized by early inhabitants, poorly equipped, with tools. The next use was in the manufacture of lime, which was employed by the ancients in mortar. These two uses of limestone are still all important, but they have been overshadowed in scores of regions by literally hundreds of new applications for raw lime-stone or products made from it. Anyone familiar with modern manu-facturing processes can quickly call to mind many industries in which limestones are essential, and new uses are continually coming to notice. Any enumeration would probably be incomplete and soon out of date.

Jan 1, 1935