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By E. A. Gulbransen, J. W. Hickman

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By MERLE HOWARD GUISE

WHEN I was a boy I walked into Fairbanks in 1905. I was but a soft chechako, and arrived with blisters covering my feet, as a result of "mushing" the 400-mile trail on foot. Because of them, the display windows of the trading posts were first to catch my eye-dog and horse collars, harness and sled parts! And because of my enthusiasm for things adventurous, I looked long upon the prospectors' gold pans, shovels, rifles, camp equipment, and what not. Today those windows are filled with motor car accessories, tires and repair parts; yes, even thermos bottles and vacuum cleaners! There were many chance meetings with little parties of prospectors in my youth, and it always set my blood to tingling. Sometimes it was a 70-year-old sun-baked son of the Arizona desert, wrangling his stubborn, faithful jenny away from some outfitting store, at others a shovel-ended poling b0at in northern Canada, \vith the partners and the dogs towing upstream along the bank, or an old sourdough, with tug-rope around neck and hand on the spruce sapling gee-pole, mushing along behind his two or three old, plodding malamutes, dragging a little Yukon sled piled high with rusty sheet-iron stove, pick and shovel, cross-cut saw and axe, rifle, bales of dog salmon, and other paraphernalia. These meetings envisioned the panning of old creek beds and draws in the search for as yet undiscovered pay-channels; they meant the toughest kind of work sinking a hole to bedrock in some far-away valley of promise; they suggested wood fires to thaw the frozen muck and gravel and crude windlass and hand-made tub to hoist the water and the mud; but loudest of all they spoke of Adventure.

Jan 1, 1929

By George W. Powel

IN the nation's effort to raise its magnesium metal supply to meet the ever increasing demand, the Government is relying not only on standard established practice but has extended its support to developments not so well proved-at least, not commercially proved. Within the past few months considerable progress has been made, not only in the definite output of metal but in the exploitation of new processes, the successful adaptation of which should, in a reasonably short time, assure an adequate supply of magnesium. Recent months have also witnessed a reshuffling of the favored methods as well as of the likely raw materials, with the mineral dolomite gaining in interest over its richer but less abundant competitor, magnesite, while the lowly sea water appears to be losing ground to the higher magnesian brines of Michigan and western Texas. Every month sees a new alignment and there are signs that still newer methods or raw materials will be in use before the industry finally stabilizes itself.

Jan 1, 1942

By Charles E. Heinrichs

IN the last decade one of our oldest and largest non-metallic metallic mineral industries has been the subject of persistent technical research, the results of which are another example of the benefits following the systematic application of scientific principles. The consequent improvement in the technique of phosphate recovery represents the greatest material advance in the industry since the discovery of phosphate in Florida in 1881. Moreover, these successes have stimulated interest and development in numerous other nonmetallic industries. Strange as it may seem, and despite the fact that the phosphate deposits of Giles County, Tennessee, together with those of Polk and Hillsborough Counties, Florida, have yielded more than 50,000,000 long tons in the last twenty years, the mineralogy of phosphates has been given scarcely any space in our technical literature. For many years it was the general consensus that these so-called phosphate rocks represented a physical mixture composed principally of tri-calcium phosphate, together with smaller quantities of calcium carbonate, calcium fluoride, iron phosphate, aluminum phosphate and other less important constituents. More recent investigations, however, led to the conclusion that these phosphates really represent a complex mineral in which calcium, iron, aluminum, phosphorus pentoxide, carbon dioxide, and fluorine all form a definite part of the molecule. Colony, after a careful study, utilizing chemical, microscopic, and X-ray diffraction methods, reported that American phosphates consist principally of calcium-carbono-phosphate of the staffalite type.

Jan 1, 1933

By Brian R. Castle, James J. Scott

INTRODUCTION Referring to a ground support system as a 'band-aid' borders on getting cute, but the application of cable slings in U.S. mining is somewhat analogous. Where problems in the roof or rib require additional support, the versatile cable sling is the answer in a variety of conditions. To fully understand how and why cable slings are used today we must briefly review their development history. Much of the thrust over the last five to seven years in ground support fixtures has been the development of hybrid systems. Taking the best of two or more existing roof bolt fixtures and marrying them into a new fixture which exhibits the good characteristics without the bad of the parent systems. Resin point anchored mechanical bolts, continuous threaded rebar bolts, and others have all be- come important fixtures in rock mass stabilization. HYBRID GROUND SUPPORT SYSTEM The cable sling system is also a hybrid, both in its parentage and in its ground support characteristics. See figure 1. Cable slings combine the techniques of cement. grouting high-strength cables, Friction Rock Stabilizers, and truss-like suspension into a versatile and high- strength ground support system. 1/2" high-strength cable is cement grouted in place in a manner similar to pre-

Jan 1, 1983

By J. Murray Riddell, George A. Morrison

THIS paper is a companion to the one by George A. Morrison on Mining a Deep Limestone Mine in Ohio.[+] Barberton is 8 miles west of Akron, Ohio, and 23 miles south of Cleveland. The underground mining of limestone at Barberton constitutes the world's deepest limestone mine. The stratigraphy is as follows: 0-20 ft. Loam, clay, sand and gravel. Water bearing. 20-40 ft. Fractured. sandstone. Water bearing. 40-110 ft. Sandstone with interbedded shale, slightly fractured. Water bearing. 110-314 ft. Sandstone with interbedded shale, slightly fractured. Water carrying. 314-2197 ft. Shale with occasional seams of sandstone, which varies in thickness from a few inches to 4 feet. Dry. 2197-2247 ft. Limestone. Dry. 2247-2742 ft. Dolomitic limestone. Dry. 2742-2767 ft. Salt. Dry. 2767- Dolomitic limestone. Dry. All of the strata dip to the southeast, about 0.5 per cent from the horizontal. The top 110 ft. of the crust is water-bearing. The rock strata are naturally fractured to a depth of 314 ft., sufficient to allow the passage of water. In the shaft-sinking operations, a stra was encountered at a depth of 520 ft., and flows of methane gas were pierced at depths of 1350 and 1952 feet. Specifications for the mine plant called for, in part, the sinking of two vertical shafts and a hoisting plant capable of producing at the rate of 300 tons per hour. No. I shaft is 550 ft. west of No. 2 shaft. Each shaft measures 8 by 17 ft. outside of steel. General features of the design (Fig. I) are: Principal set members, 6-in. H-section; connecting angles (studdles), 3/8 by 4 by 4-in. angle irons; spacing of sets, 8 ft. centers; spacing of bearer sets, generally, 160 ft.; bearers, of 12-in. I-beams. Each bearing set featured a concrete ring about the periphery of the shaft, steel to rock, and 8 ft. in height; permanent guides, 6 by 10-in. long-leaf yellow pine, 85 per cent heart. THE SHAFT-SINKING OPERATION The preliminary shaft-sinking work consisted of driving interlocked steel piling about the exterior of the shafts to depths of 35 and 32 ft., respectively, and of such horizontal dimensions as to ultimately permit the pouring of a concrete collar 2 ft. in horizontal thickness. Following the pouring of a shaft collar, a temporary wooden headframe for shaft-sinking purposes was erected. The head-frame, while ordinary, featured: (I) a storage pocket of 300 cu. ft. capacity with truck servicing facilities, and (2) pneumatically operated dump doors, which were actuated by the hoistman, thus caring for the dumping of the "ball-and-chain"

Jan 1, 1944

By H. M. Chance

STRETCHING from New York southwestwardly to Georgia is a great range of hills and mountains consisting of pre-Palaeozic schists, slates, and gneissic and granitoid rocks, known locally by many different names; in Pennsylvaniaa as the South mountains, the Berkshire or Durham and Reading hills, and in Virginia and farther south as the Blue ridge. To the northwest of this range lies the " Great Valley," underlain by Lower Silurian limestones, and known as the Lehigh valley, Cumberland valley, Shenandoah valley, valley of Eastern Tennessee and Georgia and by other local names, but all these are parts of one valley, geologically and geographically continuous from New Jersey to Georgia. Lying upon and along the northern flank of this range of mountains, and dipping northwestwardly under the limestone of the valley, is the Potsdam formation (Primal or No. 1 of the Pennsylvania Geological Survey), which consists of sandstone or conglomerate overlain by slates. The latter are sometimes arenaceous and occasionally are replaced in part by sandstone. This formation varies from a few feet to several hundred feet in thickness. At the outcrop the slates are completely decomposed, oxidized or disintegrated, forming a belt of clay several hundred feet wide occupying the interval between the outcroppings of the sandstone and limestone. This clay-belt includes a more or less continuous series of iron-ore (brown hematite) deposits, which have been, and still are, extensively worked. The belt is more or less continuously mineralized with iron throughout its length, and hundreds of large deposits of ore have been developed and worked, producing many millions of tons of ore.

Sep 1, 1908

By John V. Beall

Since the U. S. Metals Refining Co. works was established, around the turn of the century, near the town which is now called Carteret, N. J., it has grown to be a major producer of refined copper and the main source of that special brand known as "oxygen-free high-conductivity copper." Owing to the complex metallurgical problems arising from handling a variety of raw materials such as copper concentrate from Matahambre, Cuba, copper and brass scrap from the New York area, and domestic blister copper, the organization is geared from top management down through its 2000 employes to maintain a high degree of flexibility in plant operation. The Company is a subsidiary of The American Metal Co. Charges for the smelter furnaces, one reverberatory furnace and one blast furnace, are made up in. bedding bins so that they may be tailored to the production of a constant grade of blister copper. The reverberatory furnace smelts the .sulphide charge, which may be a blend of ten different materials but principally the Cuban concentrate, and the matte from the process is poured into a converter. This reverberatory is 80 by 20 ft, silica lined with a slag bottom, fired by pulverized coal, and continuously side-charged from the top by bottom-dump cars which keep the side walls covered. It produces a 40 to 50 per cent copper matte. The fuel-charge ratio is 4.35 tons of solid charge per ton of coal. The furnace has a capacity of 10,000 tons of charge per month and produces from 5000 to 6000 tons of slag per month which must be disposed of. About 5000 tons of converter slag is produced monthly and returned molten to the reverberatory furnace. The converter gases go through a spray chamber to a Cottrell precipitator and thence to the flue system. Smoke from the

Jan 1, 1948

By J. Murray Riddell, George A. Morrison

This paper is a companion to the one by George A. Morrison on Mining a Deep Limestone Mine in Ohio.‡ Barberton is 8 miles west of Akron, Ohio, and 23 miles south of Cleveland. The underground mining of limestone at Bar-berton constitutes the world's deepest limestone mine. The stratigraphy is as follows: 0-20 ft. Loam, clay, sand and gravel. Water bearing. 2-40 ft. Fractured sandstone. Water bearing. 40-110 ft. Sandstone with interbedded shale, slightly fractured. Water bearing. 110-314 ft. Sandstone with interbedded shale, slightly fractured. Water carrying. 314-2197 ft. Shale with occasional seams of sandstone, which varies in thickness from a few inches to 4 feet. Dry. 2197-2247 ft. Limestone. Dry. 2247-2742 ft. Dolomitic limestone. Dry. 2742-2767 ft. Salt. Dry. 2767- Dolomitic limestone. Dry. All of the strata dip to the southeast, about 0.5 per cent from the horizontal. The top 110 ft. of the crust is water-bearing. The rock strata are naturally fractured to a depth of 314 ft., sufficient to allow the passage of water. In the shaft-sinking operations, a stra- turn of oil-bearing sandstone one foot thick was encountered at a depth of 520 ft., and flows of methane gas were pierced at depths of 1350 and 1952 feet. Specifications for the mine plant called for, in part, the sinking of two vertical shafts and a hoisting plant capable of producing at the rate of 300 tons per hour. No. I shaft is 550 ft. west of No. 2 shaft. Each shaft measures 8 by 17 ft. outside of steel. General features of the design (Fig. I) are: Principal set members, 6-in. H-section; connecting angles (studdles), ? by 4 by 4-in. angle irons; spacing of sets. 8 ft. centers; spacing of bearer sets, generally, 160 ft.; bearers, of 12-in. I-beams. Each bearing set featured a concrete ring about the periphery of the shaft, steel to rock, and 8 ft. in height; permanent guides, 6 by 10-in. long-leaf yellow pine, 85 per cent heart. The Shaft-sinking Operation The preliminary shaft-sinking work consisted of driving interlocked steel piling about the exterior of the shafts to depths of 35 and 32 ft., respectively, and of such horizontal dimensions as to ultimately permit the pouring of a concrete collar 2 ft. in horizontal thickness. Following the pouring of a shaft collar, a temporary wooden headframe for shaft-sinking purposes was erected. The head-frame, while ordinary, featured: (1) a storage pocket of 300 cu. ft, capacity with truck servicing facilities, and (2) pneu matically operated dump doors, which mere actuated by the hoistman, thus caring

Jan 1, 1946

By T. L. Joseph

A DEMAND for specialized knowledge has directed engineering curricula towards competency in some particular field or occupation. Preparation for life in a broad sense of completeness has received little consideration. Ways and means are needed for weaving some of the threads of liberal education into the fabric of engineering education. Any effort to develop a humanistic-social stem of engineering education will depend largely upon the content of the courses and the type of instruction offered. Many of the courses in college curricula are intended to lay a foundation for more advanced courses to be taken later by those. who specialize in some particular field. Students in other fields lack the background necessary to take the advanced courses and have too much detailed information, soon forgotten, forced upon them if they pursue the foundation courses. To develop a humanistic-social stem for engineering education existing catalogue courses selected should follow some general plan aimed towards broad educational objectives. Courses packed with detailed factual information are necessary for the stu-

Jan 1, 1947

By C. E. Stafford

and tougher, and will carry double the tonnage of any of Dr. Dud ley's soft mils. C. E. Stafford, Steelton, Pa.: I must confess my high ap preciation of Dr. Dadlq's conscientious and painstaking work, and of his scientific methds in obtaining the data; but with his method of handling these results and with his conclusions drawn therefrom 1 canuot agree. The reasons for this difference of opinion I will endeavor to explain. It is apparent on inspecting his Plates 6 and 7 that the majority of the slower-wearing rails are from the north track, and generally have a longer time of service, a greater average tonnage per rail, and a smaller avernge tonnage per year per rail than the faster wearing, the majority of which are from the south track, and gener ally have a shorter time of service, a smaller average tonnage per rail, and a greater average tonnage per year per rail. Have these facts any significance Have these different of conditions to which they are subjected any baring on the relative wearing capacity of these rails I venture to say they have. I think, after a study of Table I (page 676), (an arrangement of linee 17 and 18 of Plate a), in connection with Plates 6 and 7, we will find that the slower wear of the 32 best rails is only partly due to qualities inherent in the rails themselves, but is principally due to external conditions favorable to slower wear. In regard to the north and south track, we know that over the rsoiith track come the loaded cam from the West, and that over the north track these cars return, most of them, empty. It is evident that this means for the north track a less average tonirage per rail per year; or, in other words, a lower wheel tonnage. When the load per wheel is less, the resistance and consequently the wear must, necessarily, be less, other things being equal. Time of service, alee, has an important bearing on the question in hand. It has been only within the last five or six years, as Dr. Dudley has pointed out, that the roadbed of the Pennsylvania Rail road has reached its present admirable condition. Before this time the njadbrd was more elastic, more yielding (and probably not uni tbrmly so) than at present. These circumstalices might cause a sofier rail to be more durable than a harder one, owing to the fact that it ulonId yield rnore or less to the bending force of the passing load and would thus get a bearing on each cross-tie. The harder rail, on the other hatid, being stiffer and more. unyielding, would not

Jan 1, 1881

By Walter R. Hibbard

ALTHOUGH extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110), [III] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampon5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr s in a standard mercurous nitrate test. Edmunds 12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wassermann reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. PREPARATION OF SPECIMENS Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5,10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. DETERMINATION OF POLE FIGURES A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pct nitric acid to 0.0015 in. thickness and (III) pole figures were determined using copper K-alpha radiation in the manner described by Brick.1 The three general types of pole figures

Jan 1, 1947

By Joseph W. Richards

ALTHOUGH bad grammar, the above query is probably, at the present moment, good sense. Why was the Institute started and why does it continue to exist? The small group of men who worked out the original idea felt keenly the necessity of mining engineers and metallurgists getting together in order to discuss their professional problems. That necessity still exists but it does not strike the present generation of engineers so keenly because they have always had the Institute: they do not know what it is to be without it. The Institute is a great graduate school of mining and metallurgy. All of its members who have something to say worth saying are the teachers; all the rest may be learners or critics. No university or technical school can match the experience and information which the authors of its papers possess, no institution of learning has a body of potential listeners so extensive and so vitally interested.

Jan 1, 1921

By Philip B. Bucky

WITH the exhaustion of the sections of iron ore bodies amenable to opencut mining the iron ore miners raise the question: "How can we mine the extensions of these ore bodies in depth with the same costs as obtained in opencut work?" This question brings to the fore the relationship between mineral exploration and research on mining procedures. The iron miners must either find new de? posits amenable to their known methods of mining or develop new mining methods for deep deposits. It is understood that the oil companies will spend $30,000,000 next year in the search for new oil fields. How much the metal mining companies will spend in the search for new ore bodies is unknown, but without doubt the amount will run into several millions of dollars. If the mining companies that concern themselves with metals, nonmetallics, and fuels will set aside a substantial sum for fundamental and applied research in mining methods, they can not only lower their costs but increase their reserves thereby. Any increases in mining efficiency automatically result in increased ore reserves at no cost.

Jan 1, 1947

By W. F. Dietrich

Mineral fillers are relatively inert chemically under the conditions of use but have physical properties* that modify those of the materials • The properties. uses, and other data on 15 classes of important *The pro listed in the second edition of Industrial Minerals and Rocks.l A third edition of this reference is in preparation. in which they are incorporated. The mineral fillers considered in this article are asbestos, barite, clays, diatomite, crushed limestone, limestone whiting and lime, mica, silica, talc and soapstone, and pyrophyllite. Slate and stone, other than limestone and its derivatives, are excluded because, even though used in large quantities, they are exceptionally low-cost materials generally produced close to the area where they are used. Carbon black is excluded because it is manufactured from natural gas and more than 90 pct of the output is used in rubber; hence the factors for estimating requirements are easily evaluated. OVERALL GROWTH FACTORS Table I gives the population, retail sales, and value added by manufactures in the U. S. and in the eleven western states in 1954. These data are rough guides to the proportionate part of total U. S. markets for products containing mineral fillers that may be expected in a given area. For example, the population of the eight Mountain states in 1954 was 3.6 pct, and retail sales in these states were 3.8 pct of the U. S. total, but the value added by manufactures was only 1.3 pct of the U. S. total. On the other hand, the three Pacific Coast states, with 10.3 pct of the total population, had 12.0 pct of the retail sales and produced 9.6 pct of the value added by manufactures. On an industry-by-industry basis the correlation between the three guideposts will not be as close as shown in the 1954 data for the Pacific Coast states, but in the long-term view the continuing rapid population growth in the western states is certain to result in expanded industrial production at an even more accelerated pace, which will shorten the gap between local consumption and production in most major groups of manufactured consumer goods. Of course, there will always remain favorable areas for production of specific products. Such special situations must be individually analyzed. Fig. 1 compares the population trends in the U. S., the western states, and California with Real Gross National Product from 1910 to 1957, with forecasts to 1970. It is estimated' that the U. S. Real Gross National Product, as measured by the value of goods and

Jan 1, 1960

By Edward Steidle

NOTHING stands still. We go forward or backward. As a distinct group of educators, our immediate concern is with the preparation of young men and women for participation in the mineral industries on a professional basis. I am going to have the temerity to state emphatically that for a long time as a whole we have remained in a static position. We are now confronted with the choice of advancement or retrogression. We are still in a position to make a choice and our ultimate fate will depend upon the course of action we elect to follow. Wars always have been great catalysts and social and scientific advancements mature under military stimulus in a fraction of the time normally consumed. We are now in the midst of a conflict whose duration or final effects cannot be estimated. However, the record already demonstrates that this war as never before is a mineral war in which incentive, strategy, and outcome are directly related to the distribution and utilization of minerals. The inevitable result is a drain upon our resources now reflected in our record production and a growing public consciousness of the importance of minerals in the role of human affairs. It is evident that we must seek new mineral frontiers beyond the borders of the United States and take every other precaution to forestall a "have-not" position in the world.

Jan 1, 1943

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By T. M. Morris

G. L. Simard and D. J. Salley—The authors and ourselves" independently came to similar conclusions both as to the value of tracer methods for the study of flotation and the general nature of collector-mineral interaction. The dodecylamine-quartz system appears to be simpler than the dithiophosphate-galena one, and the results therefore appear clearer. It is evident from a comparison of the two papers, however, that care must be used in extending the results to other more complicated systems. In the case of dodecylamine-quartz, the possible influence of micelle formation is of interest. There is no a priori reason why complete monolayer formation should necessarily occur at the concentration for micelle formation, since sorption depends on the nature of the substrate as well as on the properties of the solute in solution which alone determine micelle formation. Indeed, the fact that the onset of increased adsorption, point B in fig. 2, occurs at a concentration one tenth the critical value for micelles might imply that micelle formation does not have an influence. Interestingly enough, the data may be handled by the methods used for multilayer adsorption of gases on surfaces. Thus, if the amount adsorbed is plotted versus concentration, a sigmoid type curve is obtained, similar in form to a so-called Type I1 isotherm13 generally attributed to multimolecular adsorption. A monolayer value of about 0.12 mg per g may be estimated from the knee of this isotherm. On the other hand, if a plot is made according to the multilayer gas equation for adsorption to an unrestricted number of layers, eq 38,13 assuming the critical micelle concentration as the saturation concentration, the data above 120 mg per liter fall on a straight line from which a monolayer adsorption of 0.3 mg per g results. These considerations suggest that the monolayer may occupy an area somewhat less than the geometric value of 0.4 mg per g, and that micelle formation may indeed be a factor in the adsorption. the angle between the solid-liquid and liquid-gas interfaces, measured through the liquid. The value of the equilibrium contact-angle is uniquely determined by the value of the interfacial energies of the three intersecting interfaces and is independent of other forces in the system. When the liquid-gas interface intersects the solid at an edge—as was the case for all the experiments reported in this paper—the orientation of the solid-liquid interface is indeterminate or varies through 90" for a right-angle edge. Mr. Morris has called the angle between the horizontal and the liquid-gas interface for this edge condition a "static contact-angle." I feel that this term is unnecessarily misleading. In the first place, "static contact-angle" sounds too much like "equilibrium contact-angle." In the second place, the magnitude of the "static contact-angle," which I would prefer to call the "supporting angle," is determined by the forces in the system other than those derived from the interfacial energies, hence "contact angle" is misleading. If Mr. Morris had said that the "supporting-angle" is variable and depends on the weight of the particle and size of the bubble and that it has a maximum possible value equal to the equilibrium contact-angle, his discussion would have been more accurate. T. M. Morris (author's reply)—Mr. Kellogg puts forth a reasonable criticism of some of the terminology used in the paper. I agree that the term "static contact angle" may be misleading. Substitution of the term "supporting angle" or "vector angle" may be more suitable. F. X. Tartaron—In this paper the author presents a very interesting mathematical development of the forces present when a mineral particle adheres to an air bubble. Excellent concordance is obtained between mathematical formulation and experimental results. It is the writer's understanding that when the mineral surface presented to an air bubble is greater than the area of contact, the maximum contact angle is obtained. However, this contact angle represents distortion of the bubble, the normal shape of which is spherical or in cross-section, circular. This distortion produces a force that acts in opposition to the force of adhesion between the bubble and particle. Hence, at maximum contact angle, the force of adhesion between bubble and particle is at a minimum for static conditions. However, when the size of bubble is increased, the size of particle remaining the same (and all other conditions remaining the same), the contact angle decreases, the distortion of the bubble decreases and the force in opposition to adherence of bubble and particle also decreases. Thus, there is stronger attachment between bubble and particle. When this situation is applied to actual flotation conditions, it is doubtful that it has any significance. The reason is that the bubbles are normally so much larger than the particles, that in substantially all cases, it is probable that negligible distortion of the bubble takes place. In table IV, the author makes computations for bubbles from 0.50 to 2 mm diam. This is from 0.02 in. to 0.08 in. Certainly the bubbles generated in a flotation machine are far larger than this. The surfaces of the author's bubbles range from 0.79 to 12.6 sq mm. The area of contact of the glass rod (0.15 mm diam) is 0.017 sq mm. Thus, ratio of bubble surface to mineral area of contact ranges from 47 to 741 in round numbers. If we take a %-in. diam bubble and a 65-mesh (0.208 mm) particle of cubical shape, the ratio of bubble surface to mineral area of contact is 2931. Mineral particles do not readily become attached to air bubbles. Taggart has shown that in pneumatic flotation machines collector-coated particles are only temporarily attached to bubbles. They keep falling off and down in the froth but at a delayed rate as compared with gangue. Spedden and Hannan's motion pictures confirm the difficulty of attaching particles to air bubbles. In the agitation froth process, according to Taggart, air is precipitated from the water selectively on to the collector-coated particles and these

Jan 1, 1951

By T. M. Morris

G. L. Simard and D. J. Salley—The authors and ourselves" independently came to similar conclusions both as to the value of tracer methods for the study of flotation and the general nature of collector-mineral interaction. The dodecylamine-quartz system appears to be simpler than the dithiophosphate-galena one, and the results therefore appear clearer. It is evident from a comparison of the two papers, however, that care must be used in extending the results to other more complicated systems. In the case of dodecylamine-quartz, the possible influence of micelle formation is of interest. There is no a priori reason why complete monolayer formation should necessarily occur at the concentration for micelle formation, since sorption depends on the nature of the substrate as well as on the properties of the solute in solution which alone determine micelle formation. Indeed, the fact that the onset of increased adsorption, point B in fig. 2, occurs at a concentration one tenth the critical value for micelles might imply that micelle formation does not have an influence. Interestingly enough, the data may be handled by the methods used for multilayer adsorption of gases on surfaces. Thus, if the amount adsorbed is plotted versus concentration, a sigmoid type curve is obtained, similar in form to a so-called Type I1 isotherm13 generally attributed to multimolecular adsorption. A monolayer value of about 0.12 mg per g may be estimated from the knee of this isotherm. On the other hand, if a plot is made according to the multilayer gas equation for adsorption to an unrestricted number of layers, eq 38,13 assuming the critical micelle concentration as the saturation concentration, the data above 120 mg per liter fall on a straight line from which a monolayer adsorption of 0.3 mg per g results. These considerations suggest that the monolayer may occupy an area somewhat less than the geometric value of 0.4 mg per g, and that micelle formation may indeed be a factor in the adsorption. the angle between the solid-liquid and liquid-gas interfaces, measured through the liquid. The value of the equilibrium contact-angle is uniquely determined by the value of the interfacial energies of the three intersecting interfaces and is independent of other forces in the system. When the liquid-gas interface intersects the solid at an edge—as was the case for all the experiments reported in this paper—the orientation of the solid-liquid interface is indeterminate or varies through 90" for a right-angle edge. Mr. Morris has called the angle between the horizontal and the liquid-gas interface for this edge condition a "static contact-angle." I feel that this term is unnecessarily misleading. In the first place, "static contact-angle" sounds too much like "equilibrium contact-angle." In the second place, the magnitude of the "static contact-angle," which I would prefer to call the "supporting angle," is determined by the forces in the system other than those derived from the interfacial energies, hence "contact angle" is misleading. If Mr. Morris had said that the "supporting-angle" is variable and depends on the weight of the particle and size of the bubble and that it has a maximum possible value equal to the equilibrium contact-angle, his discussion would have been more accurate. T. M. Morris (author's reply)—Mr. Kellogg puts forth a reasonable criticism of some of the terminology used in the paper. I agree that the term "static contact angle" may be misleading. Substitution of the term "supporting angle" or "vector angle" may be more suitable. F. X. Tartaron—In this paper the author presents a very interesting mathematical development of the forces present when a mineral particle adheres to an air bubble. Excellent concordance is obtained between mathematical formulation and experimental results. It is the writer's understanding that when the mineral surface presented to an air bubble is greater than the area of contact, the maximum contact angle is obtained. However, this contact angle represents distortion of the bubble, the normal shape of which is spherical or in cross-section, circular. This distortion produces a force that acts in opposition to the force of adhesion between the bubble and particle. Hence, at maximum contact angle, the force of adhesion between bubble and particle is at a minimum for static conditions. However, when the size of bubble is increased, the size of particle remaining the same (and all other conditions remaining the same), the contact angle decreases, the distortion of the bubble decreases and the force in opposition to adherence of bubble and particle also decreases. Thus, there is stronger attachment between bubble and particle. When this situation is applied to actual flotation conditions, it is doubtful that it has any significance. The reason is that the bubbles are normally so much larger than the particles, that in substantially all cases, it is probable that negligible distortion of the bubble takes place. In table IV, the author makes computations for bubbles from 0.50 to 2 mm diam. This is from 0.02 in. to 0.08 in. Certainly the bubbles generated in a flotation machine are far larger than this. The surfaces of the author's bubbles range from 0.79 to 12.6 sq mm. The area of contact of the glass rod (0.15 mm diam) is 0.017 sq mm. Thus, ratio of bubble surface to mineral area of contact ranges from 47 to 741 in round numbers. If we take a %-in. diam bubble and a 65-mesh (0.208 mm) particle of cubical shape, the ratio of bubble surface to mineral area of contact is 2931. Mineral particles do not readily become attached to air bubbles. Taggart has shown that in pneumatic flotation machines collector-coated particles are only temporarily attached to bubbles. They keep falling off and down in the froth but at a delayed rate as compared with gangue. Spedden and Hannan's motion pictures confirm the difficulty of attaching particles to air bubbles. In the agitation froth process, according to Taggart, air is precipitated from the water selectively on to the collector-coated particles and these

Jan 1, 1951

By H. Conrad Meyer

The wizardry of nucleonics has added new and greater dimensions to the almost inseparable "twins"-zirconium and hafnium. So close is their relationship that neither element is found free of the other in any presently known mineral. Although zirconium in the form of its oxide was discovered in 1789 by Klaproth, the metal in an impure, nonductile form was not isolated until 1824 by Berzelius. About 100 years later -1925-van Arkel and deBoer developed and patented a technique for the deposition in vacuo of crystalline, coherent, highly ductile metal of extreme purity on an electrically heated filament through the dissociation of gaseous zirconium tetraiodide. Within the past five years both zirconium and hafnium have been dramatized by the press and in popular science magazines. This has led to the false assumption that practically all of the world consumption of zirconium ores is used in the production of the metals. Recent statistics on the subject show that not over 15 pct of the zirconium ore consumed in 1958 went to ferrosilicon zirconium and zirconium metal. The rest was consumed in refractories, foundry sand and facings and ceramics. The importance of zirconium as a component in compact, relatively lightweight nuclear energy units, such as those now used in the submarine Nautilus,6 is well established. A rival of zirconium metal as a casing for atomic fuels is a newly developed ceramic body. It is claimed to be cheaper than zirconium-to withstand higher temperatures-and to be more resistant to corrosion. Whether such ceramic casings have the required low thermal neutron absorption cross section, high strength and easy formability of zirconium is yet to be demonstrated. Hafnium, because of its low order of abundance and its close chemical relationship to zirconium, was not definitely recognized as a new element until around 1923, despite prior claims. A study of the X-ray spectra of zirconium led to its identification. The circumstances leading to the discovery of hafnium were much less fortuitous than those surrounding zirconium. The more precise tools of arc and X-ray spectrometry lent themselves admirably to the search for elements to fill certain gaps in the periodic table. [ ] Pure, ductile hafnium-a metal similar in appearance to stainless steel-has a specific gravity of 13.3 (zirconium 6.52) and a melting point of 2,200°C. In other respects it closely resembles zirconium except in one important respect which gives it a preeminent position in nuclear energy development, namely, a high thermal-neutron absorption cross section. This explains the necessity of hafnium-free zirconium in atomic piles. The ability of hafnium to capture thermal neutrons makes it an excellent "moderator" of "governor" when used as control rods in nuclear reactors (Table 1).

Jan 1, 1960