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By J. C. Febles

HISTORY. THE use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and .that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. bad been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore' had been uncovered and developed that copper sulphate began to appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 7, 1913

SEC. 1. The membership of the Institute shall comprise seven classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members; 7. Junior Foreign Affiliates. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain Members.

Jan 1, 1946

By G. Townsend Harley

STOPING methods in which shoveling plays an important part are gradually being replaced by other and cheaper methods. But there will always be considerable shoveling done underground in stopes as well as in drifts, tunnels, urinzes, and shafts. At the mines of the PhelpsDodge Corporation at Tyrone, N. M., the cost of shoveling in all stopes in 1917 amounted to 24c. per T. In the top-slice stopes for the same period, it cost 27 c. per T. or 16 per cent, of the total cost of these stopes. The tonnage for shovelers from all stoping was 9.3 T. per man, and for topslicing 8.2 T. per man. These stopes were not unduly hot, and there was not more than the usual amount of timber to interfere with the work of the men. The tonnages obtained per shoveler were considered low; first, because of a poor grade of Mexican labor, many of the men having come in from railroad grading camps; and second, because of a poor spacing of raises, especially in the top-slice stopes, where, in general, they were spaced 25 ft. by 66 ft. (7.6 by 20.1 m.) centers. The average wage per laborer shift was $2.67 during the year. It was thought, however, that even under these conditions the men were not producing the tonnage that they should, so, with the consent of the management, the writer undertook to determine how the general efficiency of the underground shoveling could be improved. No predetermined plan for conducting these experiments was arranged because we had no definite ideas as to the scope of the work or the number of elements into which the investigation would resolve itself, before all of its phases could be determined. We were sure, however, that any work that would thoroughly cover the ground would have to be in the nature of a systematic time study, combined with a course of instruction in correct shoveling methods and adequate and intelligent supervision of the work. Two or three companies in the Southwest have done some work to determine the proper shovel to be used undcrground, but so far as is known the work has been limited to equipping certain parts of their mines with a particular type and size of shovel and thereafter watching the cost and efficiency records. In each case it seems to have been the shovel that held the 21-lb. (9.5-kg.) load that gave the bcst results. Excepting personal communications from these companies, the only data available on scientific shoveling are contained in F. W. Taylor's book, "The Principles of Scientific Management," and D. J. Haucr's article, in The Contractor for March 29, 1918, "A Hundred Hints for Shovelers." This paper discusses and draws conclusions from several thousand time-study readings, taken both on the surface and in the mines for nearly a year. A sufficient number of readings were taken on each factor in the problem for the plotting of curves of the performances and to obtain accurate indices of the work to be expected from this class of labor. The work is not as complete in all of its details as we would like to havc it, because we were forced to stop the work temporarily, owing to the numbcr of men going into the National service and our inability to get others who could make time studies. The results obtained so far, however, have been of such a startling nature that we have decided to submit them at this time, subject to future modification. It is hoped, also, that a free discussion of this paper will lead to a disclosure of any errors that may have becn embodied and offer some valuable suggestions for the conduct of future work.

Jan 1, 1920

By J. M. Hodge, M. A. Orehoski

tions to which it will be subjected, and this premise is probably the most important reason for hardenability control. However, the criterion of hardenability [ ] ture after quenching should consist wholly of martensite; and that transformation of austenite to intermediate-temperature products during quenching will have a deleterious effect upon the physical properties, particularly the toughness, of the tempered material. This implies that, in order to obtain the optimum physical properties from a given steel, its "hardenability" should be high enough to suppress all transformation except that to martensite under the heating and quenching condi- IT is now generally conceded that if a steel is to develop optimum physical properties in the conventionally quenched and tempered condition, the microstruc- [ ] that at present is most widely accepted and used is based on a microstructure of 50 per cent martensite. This criterion, which was suggested by Grossmann,1 does have considerable justification. It may be readily measured by a fracture or etch test and, since it represents the point at which the hardness is changing most rapidly with variations in cooling rate, it may be determined empirically from a hardness-depth curve by determining the point of steepest slope (the inflection point. Furthermore, in plain carbon steels or in steers of low hardenability, the difference in hardenability expressed in

Jan 1, 1945

By F. B. Plummer, R. B. Newcome

The practice of introducing acid into oil wells to increase production of oil and gas has been in use since 1894, when it was first used in the Pennsylvania oil fields30.‡ It is only since 1928 that it has been used to any extent in the Mid-Continent18. The process has proved successful in increasing production, at least temporarily, in depleted oil fields where the producing formation is highly calcareous and where water drive is not too pronounced. In the Zwolle field in Louisiana, where the producing horizon is a chalk, increases of 100 per cent have been recorded25. In north-central Texas, where the oil is produced from the Marble Falls limestone, equally pronounced increases have resulted3. The production also in some fields yielding oil from quartz sand cemented with calcitc has been benefited. The evidence of actual increase in total recovery of oil, however, has been questioned by some engineers18. It has been pointed out that the results of the treatment of a well in a now district, where the process has never been tried out, can never be predicted with certainty, since other factors besides percentage of calcareous content of the oil sand play a large part in determining the success of the method. Numerous articles have been published on acid treatment and on the effects of acid on limestone1-35, yet very little has been written concerning experimental work on the actual effect of acid on capillary pores and larger oil-coated voids of oil sands. This is due partly to difficulties in duplicating field conditions in a laboratory and partly to the fact that the process has been carried out largely by contracting companies that have been unwilling to publish details of their results for fear of loss of business to competitors. The authors, using equipment developed to measure the radial permeability of oil-sand cores2', have developed a method of investigating the results of acid treatment which has enabled them to test numerous cores and to study in some detail the action of acid on the different types of rocks, particularly fine-grained rocks.

Jan 1, 1936

By F. B. Plummer, R. B. Newcome

The practice of introducing acid into oil wells to increase production of oil and gas has been in use since 1894, when it was first used in the Pennsylvania oil fields30.‡ It is only since 1928 that it has been used to any extent in the Mid-Continent18. The process has proved successful in increasing production, at least temporarily, in depleted oil fields where the producing formation is highly calcareous and where water drive is not too pronounced. In the Zwolle field in Louisiana, where the producing horizon is a chalk, increases of 100 per cent have been recorded25. In north-central Texas, where the oil is produced from the Marble Falls limestone, equally pronounced increases have resulted3. The production also in some fields yielding oil from quartz sand cemented with calcitc has been benefited. The evidence of actual increase in total recovery of oil, however, has been questioned by some engineers18. It has been pointed out that the results of the treatment of a well in a now district, where the process has never been tried out, can never be predicted with certainty, since other factors besides percentage of calcareous content of the oil sand play a large part in determining the success of the method. Numerous articles have been published on acid treatment and on the effects of acid on limestone1-35, yet very little has been written concerning experimental work on the actual effect of acid on capillary pores and larger oil-coated voids of oil sands. This is due partly to difficulties in duplicating field conditions in a laboratory and partly to the fact that the process has been carried out largely by contracting companies that have been unwilling to publish details of their results for fear of loss of business to competitors. The authors, using equipment developed to measure the radial permeability of oil-sand cores2', have developed a method of investigating the results of acid treatment which has enabled them to test numerous cores and to study in some detail the action of acid on the different types of rocks, particularly fine-grained rocks.

Jan 1, 1936

By Reinhardt Thiessen

Under sulfur in coal, is usually understood that form of sulfur which is combined with iron and known as pyrite. It occurs in the form of balls, lenses, nodules, continuous layers, thin sheets, or flakes, both in horizontal planes and vertical cleavage fissures. But pyrites also occur as very fine microscopic particles, or nodules, disseminated through the compact coal. This form has had but very little consideration. Finally, there is sulfur in coal in an amicroscopic form (not visible with an ordinary microscope), probably combined with the organic matter that exists in the coal. This form has had considerable attention from a scientific standpoint, but has probably not been recognized enough on the economic side. One or the other, or both, of these two latter forms may comprise the larger part of the sulfur content of coal, especially after it has been washed or otllerwise prepared for use. Pyrites in Microscopic Particles All coals that have been examined by the author contained a varying amount of sulfur in very small globules, or particles, of pyrite. These particles are seen in a thin [section as roughly rounded opaque dots, Figs. 1 to 10. When isolated, they are generally shown to be approximately spherical in shape, with a rough outer surface. They vary in diameter from a few microns to a hundred microns, the majority messuring from 25 to 40 microns; relatively few exceed the latter diameter. They are, therefore, very small objects. Their size is best appreciated by comparing the illustrations, in which they are shown. at a magnifiea tion of 100 diameters, with some known area like the period used in the ordinary printed page. The period is about 0.6 mm. in diameter, and . when magnified 100 times, will cover a circular area of about 2 1/2 in. in diameter, or all but the corners of the illustrations. The illustrations, therefore, represent an area about as large as an ordinary period, and the pyrite globules form but a small part of the total area. Very frequently a number of these particles are joined together in horizontal rows; oc-

Jan 1, 1920

By C. L. Bulow

In this discussion of stress-corrosion cracking of widely used copper-base alloys, no attempt has been made to prepare an extensive review or bibliography since this has been quite ably covered by other investigators. An excellent bibliography was published by H. P. croft(1)2 in connection with his studies of stress-corrosion cracking in mercurous nitrate solutions and his analyses of the magnitude and distribution of stresses in brass parts. We are reporting on a few of the results which have been obtained to date in connection with an ammonia vapor test and an alternate immersion test. These are accelerated corrosion tests for determining the susceptibility of materials to failure from season or stress-corrosion cracking due to the presence of moist ammonia and oxygen so prevalent in nature. Our experiences with the ammonia test seem to indicate that it is a more searching test, than the mercurous nitrate test.

Jan 1, 1945

By H. R. Banks

PONDERING the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote “Tho’ the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of, either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. PRINCIPLE OF BALL MILL The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely fine mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries, we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? METHODS OF GRINDING The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of fine grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1945

By Joseph Kuti

Longwall mining is the term used for the underground extraction of a wide and deep panel of coal. Such a panel may be blocked out by one or more entries on either side ("head" and "tail") of a longwall face. If all the entries are pre-driven, the panel extraction is termed longwall retreat mining. With one exception, all the longwall faces in the United States are of this type.1 Prior to the general decline in the rates of production with Continuous Miners, the development of the multiple entries generally kept ahead of the longwall extraction rate. This is no longer the case: longwall extraction rates far exceed the rate of development. In addition to this problem, in newly established mines, the development of a haulage and bleeder system based on multiple entries results in a lead-time of three years or more before longwall mining can be applied.

Jan 11, 1979

By S. F. Emmons

The first paper which appears in the published Transactions of our Institute is that read by our respected Secretary at its first meeting in Wilkes-Barre in May, 1871. It is entitled " The Geographical Distribution of Mining Districts in the United States," and presents a brief but masterly review of what was known of the distribution of our deposits of useful minerals, particularly the metals, not only from a geographical but from a geological stand-point. At the request of Dr. Raymond I agreed, somewhat hastily, perhaps, to write for this occasion a brief sketch of the geological distribution of the deposits of the useful metals in this country, in the light of the increased knowledge of the present day. In the time given no personal investigation was possible, and as it was therefore out of the question to attempt to make anything that could be considered an original contribution to the history of our ore-deposits, I have been obliged to limit myself to an examination of such pub-

Jan 1, 1894

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The properties of quenched Ti-Fe alloys have been correlated with their microstruc-tures. For specimens quenched from equilibrium in the a-ß field, the dominant micro-structural variable is the a-ß ratio. A comparison of specimens having equiaxed a-ß structures with those having acicular a-ß structures shows that the equiaxed specimens have better tensile ductility, but lower impact resistance. There is evidence to show that specimens with acicular structures reach equilibrium in the a-ß field more rapidly than specimens with equiaxed structures. Both strength and ductility are lowered by heat treatments below 700°C. IN previous work,1, 2 certain principles of the physical metallurgy of a-ß titanium alloys have been evolved. Most of these principles have been based on data obtained on alloy systems which undergo no eutectoid reaction, or in which the eutec-toid reaction is so sluggish as to be inoperative. The alloy systems previously studied included the Ti-Mn alloys, with and without a-stabilizing additions, and the binary Ti-Mo alloys. The most important of these principles are: I) The compositional factors which affect mechanical properties are solid solution strengthening, the martensite transformation, and instability of

Jan 1, 1957

SUCCESSFUL development of a new process for heat hardening of pellets made from taconite concentrates was announced by Arthur G. McKee & CO., steel plant engineering and construction firm of Cleveland, and Allis-Chalmers Mfg. Co. An order for the design, engineering, and materials for a plant incorporating the process, has been received by the McKee Co. from the Reserve Mining Co. for its new E. W. Davis Works at Silver Bay, Minn. It is estimated that this plant will cost around $19 million and when in full operation, will turn out 12,000 tons of pellets per day.

Jan 10, 1954

By N. J. Grant, K. M. Zwilsky, J. T. Blucher

DISPERSION strengthening has been studied in a number of metal-metal oxide systems. To date those pure metals available as fine particles (less than about 5 p) have received most of the attention whereas solid solution alloys, generally unavailable as fine powders, have not been examined in detail. The present work was undertaken as a preliminary study to evaluate combined effects of solid solution and dispersion strengthening. The technique used was that of dry mixing of elemental powders with the oxide, followed by a diffusion treatment to obtain the solid solution. The average particle size of the powders used was: Ni, 3.2 p (1nco B); Mo, 1.3 p (Fansteel Metallurgical Corp.); and y alumina, 0.027 \i (G. L. Cabot, Inc.). The particle size of the metal powders was determined by Fisher subsieve measurements while the size of the alumina was calculated from a surface area determination. Prior diffusion studies on small compacts pressed from mixtures of nickel and molybdenum powders with and without 7.5 vol pct A1203 indicated that diffusion was complete after sintering for 100 hr at 1800" , or 50 hr at 2250", or 20 hr at 2550° F. The progress of diffusion was followed by microstructural examination and micro-hardness measurements. Two observations made during the diffusion experiments were: 1) That diffusion proceeded faster in the presence of alumina, confirming similar findings by Seith and Loepman on "SAP'';4 2) That diffusion at temperatures above 1800°F resulted in coarsening of the alumina in agreement with results of other authors reporting on the growth of alumina in nickel above 1800"F. Similar experiments in the Ni-Cr system using 6 and 20 p Cr powders of 0.7 and 0.025 pct 0, respectively, did not result in significant solid solution formation even after long time exposures at 2550° F. It must be concluded that chromium oxide films around individual particles interfere with normal diffusion. A nickel alloy containing 5 wt pct Mo and 7.5 vol pct alumina was fabricated by dry mixing of powders, isostatically compacting at 30,000 psi, diffusing for 120 hr in dry hydrogen at 1800" F, and extruding at 1950"~ with a 30 to 1 reduction of area ratio. The resulting structure, presented in Fig. 1

Jan 1, 1963

By E. Hein, R. A. Dodd

The fatigue softening of prior strain-hardened poly crystalline copper has been determined by measuring changes inflow stress resulting from fatigue treatments. Tensile fatigue does not soften the metal, while the softening due to reversed stress fatigue depends on the extent to which fully reversed stressing is approached. True tensile fatigue is shown to be possible only in the case of long wire specimens. Annealing following fatiguing of strain-hardened metal shows that tensile fatigue is very effective in modifying normal recovery and recrys-tallization. OBSERVATIONS by Ludwik and Scheu,' Kenyon,' Polakowski and Palchoudhuri, Kemsley, and Broom and Ham,596 have shown beyond doubt that strain-hardened metals are softened by reversed-stress fatigue. To some extent the softening might be associated with a rearrangement of dislocations, but the results of Broom and Ham5 on the temperature dependency of the fatigue hardening of annealed copper, and those of McCammon and Rosenberg7 on the partial recovery at 100'C of fatigue-hardened copper suggest that point defects may be involved. Since lattice vacancies are the only species of point defect present in appreciable quantities in thermody-namic equilibrium, most attention has been accorded them in the various theories advanced to explain hardening and softening effects resulting from fatigue. Precise mechanisms remain uncertain, and while some effects may be due to single vacancies, defects arising from vacancy clusters may also contribute to the changes in properties. All types of plastic deformation result in point-defect formation, one frequently invoked formation mechanism involving the nonconservative motion of jogs formed by the intersection of, for example, mixed dislocations. But since fatigue deformation is thought to be a particularly effective way of forming point defects, additional mechanisms peculiar to fatigue must be sought. One possibility is that jogged loops contract during the unloading cycle to give rows of vacancies. A local high-vacancy concentration could conceivably promote polygonization and recovery by climb, and, therefore, could explain the fatigue softening of strain-hardened metals under appropriate conditions of temperature. Conversely, the experiments by Broom and Ham6 on the fatigue hardening of copper single crystals involving subsequent tensile testing of previously fatigued specimens, resulted in the observation of distinctly lowered yield points. This could be due to vacancy atmospheres associated with dislocations, possibly augmented by jogs on dislocations. In addition to the yield-point phenomenon, a post-yield hardening was observed, with a temperature-dependence resembling the friction-hardening of irradiated metals,9 this again suggesting a point-defect mechanism. An important development in this field has been the observation,10 by transmission electron microscopy, of high concentrations of prismatic loops in fatigued aluminum. By analogy with quenched aluminum filmso11 it seems certain that these loops originate in the collapse of vacancy clusters formed during deformation. Metals, such as copper, having a relatively low-stacking fault energy would tend to produce Frank sessile loops (in practice tetrahedral defects with stacking faults on all (111) planes) rather than the glissile prismatic loops observed in aluminum. The manner in which these various defects affect the different aspects of fatigue behavior has not yet been fully investigated. The present work was designed principally to indicate whether tensile fatigue gives rise to hardening and softening effects similar to those associated with reversed stress fatigue, and with the hope of providing additional information on the contribution of point defects to fatigue deformation. Despite the uncertain ty often associated with the interpretation of resistivity data, i.e., the relative contribution of stacking faults and other defects, such measurements are conveniently employed to study point defect pheno-

Jan 1, 1962

By Herbert Hoover

THE desire of the engineers over the last few years, growing out of their contact with public affairs, that this Institute should take a wider vision than the narrower field of technology and should apply its skill to the development of civic problems which must lay in their foundation on engineering, has led to this discussion today. Some of us in San Francisco, in discussing this question of the relation of the engineers to civic problems, raised the question as to whether or not in this national emergency it was not the duty of the Mining Engineers to bring, forward their combined skill and knowledge and experience to bear upon the problems of the coal industry. This industry, considered as a whole, is one of the worst functioning industries in the United States. It is equipped with capital, with machinery, plants and labor to a peak load at least 20 per cent. above the average necessity. This peak load, therefore, involves the use of probably 100,000 men diverted from other productive industries; it involves an intermittency of employment through its whole personnel that results not only in a long train of human woe, but results also in a higher cost of coal -to the general public. The problem of whether the industry can, by any device, be cured or even partially cured of its intermittency, is solely an engineering problem. It is therefore an apropos problem for this Institute. Your President and myself and others thought that we could best develop this discussion by calling upon men of large experience in the particular branches of the soft coal industry, to bring the facts in front of this general committee, with a view to an exhaustive discussion and perhaps subsequently the appointment of a committee to formulate those facts and such remedies as may be developed into a report that would be of constructive value.

Jan 3, 1920

By G. Willard Quick

TENSILE tests of rail steels at elevated temperatures'' have shown that certain rails, in addition to having low ductility in the well-known bluebrittle range in the neighborhood of 200° C., have marked reduction in elongation and reduction of area in the temperature range from 400° to 700° C. This range of low ductility was called "the secondary brittle range" and the phenomenon, "secondary brittleness." The question naturally arises as to whether this property of the steels would be shown by impact tests performed in the same range of temperature. If so, the impact test, as suggested by Gillett3 would be a simpler and quicker method for the routine examination of steels at elevated temperature than the tensile test. A number of investigators have reported results of impact tests on steels at elevated temperatures, in which the energy absorbed decreased with increase of temperature above 200° or 300° C. Langenberg4 performed Charpy impact tests on several steels at temperatures ranging from room temperature up to 1000° F. (538° C). His results showed an increase in the energy absorbed in specimens tested in the range from room temperature to 200° or 300° C. and then a gradual decrease in the range, 300° to 538° C., the maximum temperature used. Greaves and Jones5

Jan 1, 1932

By J. W. Hickman, E. A Gulbransen

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 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

Section 67 Department of Conservation and Development, State of New Jersey, State House Annex, Trenton, N. J. H B Kummel, State Geologist For lists of publications, maps and geologic folios, address the above. Where price of postage is noted, in the following list of available publications on geology, the postage is only to New Jersey and

Jan 1, 1933