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By George W. Maynard

IN the biographical notice of Thomas F. Witherbee, published in Bulletin No. 32, August, 1909 (p. xxv), it is said that ". he is believed to have been the first manager in America to use the chemical laboratory for the purpose of controlling the regular running of the blast-furnace." Since the year is not given, I cannot decide as. to Mr. Witherbee's priority; but the statement leads me to contribute a bit of history, showing an early departure from the "rule-of-thumb " blast-furnace work to the employment of a chemist. In the autumn of 1868 the department of mining and metallurgy was established at the Rensselaer Polytechnic Institute. In connection with the assay-department a laboratory was equipped for making general commercial analyses. In January, 1869, Alexander L. Holley, the manager and builder of the Bessemer plant at the Rensselaer Works of John A. Griswold & Co., the first plant erected in the United¬States under the Bessemer patents, began to send me samples of ore, pig-iron, and steel for analysis. Early in 1869 I was regularly retained as chemist for the Rensselaer Works; and while the laboratory was not located at the works, for all practical purposes it was the works-laboratory. The increase in work soon made it necessary for me to secure an assistant. I applied to Prof. Charles F. Chandler, who recommended Dr. August Wendel, who had been an assistant of Rammelsberg and had lately landed in New York. Dr. Wendel remained with me until 1873, when I left Troy. My leaving made necessary the erection of a laboratory at the Rensselaer Works, which, was done under my supervision, and Dr. Wendel was employed as chemist. During the period from 1868 to 1873 my work as consulting mining engineer frequently called me to the Lake Champlain

Nov 1, 1909

By Robert D. Longyear

IN MOST diamond core drilling the primary objective is the recovery of samples to be used for chemical analysis, physical tests, or visual inspection. Unless these samples are reliable and the information systematically recorded, the time and money spent in securing them are largely wasted. A properly taken diamond-drill sample is similar to a properly moiled channel sample but more accurate. No channel sample can be moiled in as even a groove as the smooth cylinder of material normally removed in diamond drilling. More important still, sampling by the diamond drill practically eliminates that personal equation which Jora1emon4 reference numbers apply to publications listed in the bibliography at the end of this article) has aptly termed "the almost magnetic attraction of the most conscientious hand toward rich pieces of ore."

Jan 1, 1937

By S. Whinery

In these times of sharp rivalry, both as to price and quality, among the makers and venders of engineering explosives, it is often desirable to be able to determine the relative energy or value of the various explosives offered for sale, in order to purchase intelligently ; or, having contracted for a large amount of an explosive of a certain standard quality, to be able to ascertain if the manufacturer keeps his product up to the specified standard. The simple and inexpensive apparatus described below was devised by the writer while engaged on the improvement of the Tennessee River, at MuscleShoals, under the direction of' Major W. R. King, U. S. Engineers, in the summer of 1879. It answered the purpose so well that it is thought that a brief account of it may be of interest to other engineers. It consisted, essentially, of an old blacksmith's anvil and a common striking hammer, such as is used for driving rock-drills. The anvil was placed face downward on solid, level ground. In what was then the top of it, a vertical hole, one and one-fourth inch in diameter and about one arid three-fourths inch deep, was made with a ratchetdrill. The surface of the anvil immediately around the drill-hole was made as true and smooth as possible with a file. Next, a new striking-hammer, weighing nine pounds, with a turned and true face, was selected ; and a handle, eleven feet long and about one and a half inches in diameter, was fitted into it so that it

Jan 1, 1886

By AIME AIME

IN accordance with the custom of recent years, the Institute joined with the Western Division of the American Mining Congress in holding a joint meeting at Joplin on Sept. 28, 29 and 30. Actually the meeting might be said to have begun on the 27th, since the Engineering Education Committee held two sessions on that day, which are reported on another page. In addition to these sessions there were informal gatherings in the Hotel Conner, which was the headquarters, on the golf links and elsewhere of all those who had arrived by Sunday morning. The technical sessions were formally opened on Monday morning by Robert E. Tally who, after suitable preliminary remarks, introduced A. Scott Thompson, of Miami, Okla. Mr. Thompson in welcoming the visitors to the Tri-State district said that it had come to be known as a poor man's country and at the present price of zinc did not find it difficult to live up to its name. He also referred to the work Mr. Tally had done for the stabilization of the mineral industry. H. Foster Bain, in responding to this address for the Institute, said that mining men generally felt at home in Joplin, that the solutions of their problems and the general practice that had been developed in the district were not only of great interest to them, but that visitors could learn much

Jan 1, 1931

By J. F. Wolff

During the past 4 or 5 years, much has been added to the detailed geologic knowledge of the Mesabi Range. This has not been in the direction of discovery of any new fundamental facts, but of detailed study, subdivision and correlation of different parts of the whole formation and of individual orebodies. Prior to this time, mining engineers in the district were so engaged with the commercial interests of exploring and developing orebodies that close geologic study and subdivision were done in a few instances only. The demand for refinement of work in .this direction has led 'the engineers of the Oliver Iron Mining Co. to do extensive structural subdivision and correlation in all exploration work during the past 4 years. Such work has become a commercial necessity rather than a scientific refinement, and at the present time is being extended to all parts of the Range. In the summer of 1914, the author of this paper wrote a series of articles on the orebodies and special features of the Mesabi Rangc, which was published in the Engineering and Mining Journal, issues of July 17 to Aug. 7,1915. Since that time studies of subdivision of the iron-formation have been extended considerably. The principal feature of this paper is the presentation of the subdivisions of the iron-formation. To this is added a discussion of the relations of the orebodies to the gentle folding and fracturing of the formation, and special features of the Range. The outline will be as follows : I. General geology. 11. Subdivision of Biwabik iron-formation. 111. Relation of orebodies to folding and fracturing of the iron-formation. IV. Special features. Acknowledgnlent is due to W. J. Olcott, President, and John Uno Sebenius, General Mining Engineer, of the Oliver Iron Mining Co., for permission to use the information presented in this paper.

Jan 1, 1917

By Burt A. Waite

The new OSM regulations for ground water monitoring of underground coal mines have been the source of many concerns for the mining industry. Because the regulations were initially written at the federal level, but are being administered at the state level, considerable confusion still exists within the industry as to what is really required. Based on submission and/or approval of more than 30 monitoring plans for existing mines in Pennsylvania, West Virginia, and Ohio, three basic sections are necessary. They are: 1. background data on the hydrogeologic setting of the mine, 2. the monitoring plan itself, and 3. mining procedures to minimize adverse effects on ground water. Like all of the OSM requirements, ground water monitoring will be a new burden the coal industry must bear, but with proper planning and communication with the regulatory authorities it need not be as bad as originally feared.

Jan 1, 1983

By R. J. Stevens

THE Roan Antelope Smelter commenced operations in October, 1931. As originally designed, its equipment consisted of one reverberatory furnace, 120 X 25 ft, two Peirce-Smith converters 12 X 20 ft, and one straight line casting machine. Since that time the following additions have been made: One reverberatory furnace 120 ft X 28 ft (1934) One reverberatory furnace 95 ft X 28 ft (1943) Two 12 X 20 ft Peirce-Smith converters (1934 and 1938) One 13 X 30 ft holding furnace 6 (1938) One straight line casting machine and 2 ladle tilting quadrants (1934) The metallurgy of the smelting process is comparatively simple. However, there are several features of operation which are uncommon to most copper smelters: (1) The high grade of concentrate treated; this has always been about 50 pct copper. (2) The high flux burden on the charge. This is necessary because of the deficiency of bases'in the concentrate and the high alumina content of the concentrate. (3) The frequent necessity of adding coal to the furnace charge to control the matte grade. (4) The high grade of matte produced. This has led' to unusual converter problems. From the commencement of operations, the ore mined has come from the Roan Basin orebody. The concentrate produced from this ore consists mainly of chalcocite and shale with small proportions of other copper minerals. As mining operations extend to the Roan Extension orebody, the proportions of bornite and chalcopyrite in the concentrate will increase with a corresponding decrease in the copper content of the concentrate. Because of the concentrate grade the capacity of the reverberatory . furnaces in terms of tons of copper produced per ton of coal burned is high.. This ratio is usually over 2.2, and on especially favourable runs has reached 2.6. Reference to Table , shows that the iron content of the concentrate is unusually low. Only part of this iron is available for slag formation, the balance going to the matte. To make up this deficiency in bases, limerock is added to the furnace charge. This flux ensures a slag that is of the correct silicate degree, is sufficiently fluid, of low specific gravity, and it counteracts the thickening effect of the alumina present. An ample supply of flux is obtainable from Ndola, 2 2 miles distant by rail. Although the reverberatory slag has a high copper content, the slag fall is low and the copper loss in the slag now rarely exceeds 1.0 pct of the total copper charged. The blister copper shipped is of such purity that only one fire refining operation has been necessary to produce a wirebar with properties comparable to electrolytic copper. Bismuth has always been the most troublesome impurity and consequently the problem of its control in the finished product has been of prime importance. Practically none is removed in the reverberatory furnace. The bulk of the elimina-

Jan 1, 1947

By R. J. Stevens

The Roan Antelope Smelter commenced operations in October, 1931. As originally designed, its equipment consisted of one reverberatory furnace, 120 X 25 ft, two Peirce-Smith converters 12 X 20 ft, and one straight line casting machine. Since that time the following additions have been made: One reverberatory furnace 120 ft X 28 ft ('934) One reverberatory furnace 95 ft X 28 ft (1943) Two 12 X 20 ft Peirce-Smith converters (1934 and 1938) One 13 X 30 ft holding furnace (1938) One straight line casting machine and 2 ladle tilting quadrants (1934) The metallurgy of the smelting process is comparatively simple. However, there are several features of operation which are uncommon to most copper smelters: (I) The high grade of concentrate treated; this has always been about 50 pct copper. (2) The high flux burden on the charge. This is necessary because of the deficiency of bases in the concentrate and the high alumina content of the concentrate. (3) The frequent necessity of adding coal to the furnace charge to control the matte grade. (4) The high grade of matte produced. This has led to unusual converter problems. From the commencement of operations, the ore mined has come from the Roan Basin orebody. The concentrate produced from this ore consists mainly of chalcocite and shale with small proportions of other copper minerals. As mining operations extend to the Roan Extension orebody, the proportions of bornite and chalcopyrite in the concentrate will increase with a corresponding decrease in the copper content of the concentrate. Because of the concentrate grade the capacity of the reverberatory furnaces in terms of tons of copper produced per ton of coal burned is high. This ratio is usually over 2.2, and on especially favourable runs has reached 2.6. Reference to Table I shows that the iron content of the concentrate is unusually low. Only part of this iron is available for slag formation, the balance going to the matte. To make up this deficiency in bases, limerock is added to the furnace charge. This flux ensures a slag that is of the correct silicate degree, is suficiently fluid, of low specific gravity, and it counteracts the thickening effect of the alumina present. An ample supply of flux is obtainable from Ndola, 22 miles distant by rail. Although the reverberatory slag has a high copper content, the slag fall is low and the copper loss in the slag now rarely exceeds 1.0 pct of the total copper charged. The blister copper shipped is of such purity that only one fire refining operation has been necessary to produce a wirebar with properties comparable to electrolytic copper. Bismuth has always been the most troublesome impurity and consequently the problem of its control in the finished product has been of prime importance. Practically none is removed in the reverberatory furnace. The bulk of the elimina-

Jan 1, 1949

By George Rice

THE A.I.M.E. Ground Movement and Subsidence Committee, pro-posed in 1920, held its first technical meeting in February 1923, under the able chairmanship of Mr. H. G. Moulton. The following list of papers and discussions, indicating the scope of the problems and relation to various conditions and method of mining, were given at that meeting by the distinguished mining engineers: J. Parke Channing, on Subsidence at Miami, Arizona; Howard N. Eavenson, on Mining an Upper Bitu-minous Seam after a Lower Seam Has Been Extracted; J. J. Rutledge, on Subsidence in Two Oklahoma Coal Mines; Benjamin F. Tillson, on Caving Cracks at the Franklin Mine, New Jersey; Dr. F. W. McNair, on the Dome Theory; William Kelly, on disadvantageous effects in Mining and Back-filling Working Upward a Steep-Pitching Iron-ore Bed; Eli T. Conner, on the good results of Back-Filling by Hydraulic Means in Preventing Destructive Subsidence in the Anthracite District; Thomas H. Claggett, on the merit of Systematic Pillar Drawing in Preventing Cracks in an Upper Seam; Henry H. Otto, successful results in the anthracite district in Mining Lower Seams before Upper Seams; Douglas Bunting, on Leading Factors Incident to Successful Mining of an Overlying Seam; Edwin Ludlow, on there being "less damage to buildings when there was complete removal of coal with complete packing than when room and pillar is used without extracting the pillars"; Edward O'Toole on "bumps" in eastern Kentucky mines, which he thought were the result of geologic stresses: H. A. Buehler, on Upheaval of Surface in an Illinois Case in Advance of the Face; and R. Dawson Hall, on The Mechanics of Subsidence from Mining. The author of this paper discussed various Winds of problems of ground movement and subsidence in both metal mining and coal mining; the production of great landslides by workings near an outcrop, as at Turtle Mountain, Alberta, Canada; and general

Jan 1, 1939

By J. J. Predali, J. M. Cases

J. J. Predali and J. M. Cases (Attachè de Recherche and Charge de Recherche, respectively, Centre de Recherches sur la Valorisation des Minerais, Institut Polytechnique de Nancy, Nancy, France)-The role of CO, in carbonate flotation is one of the parameters of a complex phenomenon: the adsorption of salts of fatty acids onto minerals. The authors therefore must be congratulated for their work. Their experimental results suggest some questions: 1) Recovery with C02, benzoic acid, or HCl, look very similar [(Fig. 1)] to that with the use of air; however, the recovery decreases very slightly (<10%). But in these two kinds of experiments, two parameters are different: the pH which is near 5.8 (with C02) becomes 9.1(without C02) and the concentration of Ca* I x 10-3 mole per 1 (without C02) becomes 1.9 X 10&apos; mole per 1 (without COO. 2) Adsorption experiments (Fig. 2) permit computing the surface coverage 9 which is 7.4% (without C02) and 8% (without CO_.) for an initial concentration of 12 X 10-6 mole per 1 in sodium oleate. It seems doubtful to us that this small variation can produce large increases of the recovery in flotation. 3) It is difficult to correlate adsoption and flotation experiments because they do not seem to have been done with the same size of particles. The concentration needed to obtain 95% recovery (Fig. 1) is about 3.0 X 10_" mole per l, that is, 1.13 X 10-6 mole for about

Jan 1, 1973

ALBERT SAUVEUR, Chairman. A. A. STEVENSON, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, William Kelly, J. S. Unger, William H. Blauvelt, Charles Kirchhoff, Felix A. Vogel, James Gayley, Richard Moldenke, Leonard Waldo, Henry D. Hibbard, Joseph ANT. Richards, William R. Walker, Henry M. Howe, C. F. W. Rys, William R. Webster, Robert W. Hunt, E. Gybbon Spilsbury, Frederick W. Wood. J. E. Johnson, Jr., For the meeting of the Institute which is to be held in New York City, Oct. 16 and 17, 1913, the following program has been arranged: October 16, 1913, 10 A. M W. A. Forbes, Blast Furnace Gas Cleaning. W. H. Blauvelt, The Slagging Producer. Prof. F. Peter (Leoben, Austria), The Generation of Steam by Waste Heat from Furnaces. G. C. Stone, The Generation of Steam by Waste Heat from Regenerative Furnaces. W. R. Shinier, Over-Oxidation of Steel.

Jan 10, 1913

By Eugene A. Stephenson

NUMBER of noteworthy events in the petroleum industry may be reported for 1941, of which the most spectacular was doubtless the rise in the daily rate of crude-oil production to a peak of approximately 4,300,000 barrels. This enormous daily rate did not ensue from the furor of flush pools but represented for the most part merely a slight additional daily delivery from many wells that had previously been operated on a more restricted basis, in line with good conservation practice and also from the adroit increase in the number of days per week by the Texas Railroad Commission. Another important fact was the increase in price throughout the Mid-Continent area from the static level of $1.02 for 36°, A.P.I., crude, to $1.17 per barrel. Efforts to elevate the price above this point have met with severe opposition from the O.P.A.. as has also a similar effort by the PennsyIvania Crude Oil Producers&apos; Association, but the vastly increased costs for materials and labor may shortly give the industry the enhanced price which it has long deserved.

Jan 1, 1942

THE SOUTHWEST MINING SECTION of the National Safety. Council held a well attended two-day conference at Globe, Ariz., March 19 and 20; followed by two days of mine-rescue maneuvers at the Old Dominion mine in cooperation with the Globe-Miami District Mine Rescue and First Aid Association and the U. S. Bureau of Mines. C. L. Colburn of the Bureau had general charge of the arrangements and was chairman of the conference. All sessions were held in the Old Dominion Library. The program of papers was as follows: MINE FIRE PREVENTION AND FIGHTING What to do in Case of a Mine Fire. / Chas. A. Mitke, Consulting Mining Engineer, Bisbee, Ariz. Gunnite as a Fire Preventative. W. C. Browning, General Manager, Magma Copper Co., Superior, Ariz. Chemical Engineer&apos;s Part in Fire Fighting. Dr. L. H. Duschak, Consulting Chemical Engineer, San Francisco, Cal. Mine Fire Drills. A. C. Stoddard, Chief Mining Engineer, Inspiration Consolidated Copper Co., Inspiration, Ariz. Notes on the Installation of Fire Fighting Equipment in Mines. Benjamin F. Tillson, Assistant Superintendent, New Jersey Zinc Co., Franklin, N. J.

Jan 5, 1923

By A. Eilers

COMPOSITION OF CHARGES AND CONSUMPTION OF FUEL AT VARIOUS WORKS. A MARKED peculiarity of most of the smelting-works of the Far West is the looseness with which accounts of the operations are kept. Indeed, probably over half of the works do not keep any detailed accounts at all, the yearly gross statement of profit or loss being considered sufficient for all purposes. The reasons for this must apparently be sought in the as yet unsettled state of all business relations, and in the deplorable fact that only in isolated cases educated metallurgists are in charge of the smelting-works. Continual and regular assays of the ores, by-products, and slags, are almost unknown, so that it is impracticable to ascertain, even approximately, the losses in the smelting processes. Of cases where regular accounts are kept of the quantities of ore smelted, of the composition of charges, and of the fuel consumed, I know only two or three. Under these circumstances it is extremely difficult to collect figures which cover the operations for a considerable length of time, and which are so valuable for the metallurgist, who wishes to get an insight into the economy of smelting operations, as shown by practice. Figures obtained by personal observation, which can of course cover only the brief space of the visit of the travelling metallurgist, must, therefore, be made to replace the more valuable data. The writer has had occasion, during the last and the preceding summer, to visit the larger number of the Western lead-smelting works, and offers, in the following pages, such data relating to the economy of lead-smelting in the blast furnace at various works, as he has been able to obtain. The only object in doing so is to place these figures on record, so that they may be from time to time supplemented with other data, which are now wanting. I. EUREKA CONSOLIDATED COMPANY&apos;S SMELTING-WORKS. These works smelt the ores from the mines of the same company on Ruby Hill, Eureka, Nevada. The supply is almost unlimited,

Jan 1, 1873

By Charles Jackson Abrams

MINING is one of the major industries of the Rocky Mountain region and since the United States became involved in the present World War, all mines have been called upon by the Government for the maximum production of the strategic metals necessary. Operating under the most adverse conditions, such as priority requirements, slow delivery of necessary material and equipment, labor shortages, and freezing of all wages, which still permitted some industries to pay higher rates than were allowable in the mines, thereby drawing labor from the mines; and the United States Employment Service continually giving mine labor certificates of availability; these and many other problems made mine operation particularly difficult. Yet, in spite of these obstacles, the mining industry, either through its own resources or through Government subsidies in the form of loans or premium prices for strategic metal, have and still are making an all-out effort to meet Government demands. They, without question, have played a major role in assisting the war effort.

Jan 1, 1945

By Rossiter W. Raymond

BY the courtesy of Mr. Charles W. Jenks, of Boston, one of the owners of this interesting mine, I am enabled to lay before the Institute a suite of specimens, illustrating its peculiar formation and the paragenesis of mineral species which it presents; and a recent brief visit and rapid reconnoissance of the locality permit me to supplement this exhibition with a general description, based upon personal observation. The mine is situated upon the Culsagee Fork of the Tennessee River, in Macon County, North Carolina, a few miles from Franklin. The most practicable route by which it can at present be visited is by wagon (or preferably on horseback) from Seneca City, S. C., a station on the Charlotte and Atlanta Air Line Railroad. The itinerary is as follows: to Walhalla,* nine miles; Walhalla to Highlands, twenty-nine miles; Highlands to the Culsagee, fourteen miles. By passing the night at or near Highlands, the mine can be reached and examined and the return to Highlands made on the second day; and the round trip, if performed in the saddle, can be completed in three days from Seneca City. It is not easy, with due regard to steed and rider, to do it in less time. The rough and precipitous mountain roads do not permit rapid travel ; and the journey is at best a fatiguing one. But its slight hardships are overpaid by the stimulating effect of the climate and the great beauty of the scenery, both of which are destined to become more widely known than at present, to seekers for health and pleasure. Indeed the town of Highlands, already named, is almost entirely made up of northern immigrants, attracted by these advantages and by the inducement of cheap land for agriculture and stock-raising. The Culsagee or Sugartown fork of the Tennessee traverses the belt of ancient crystalline schists on the west flank of the Blue Ridge. This belt abounds in valuable minerals. Among those of the nonmetallic class may be mentioned graphite, soapstone, serpentine, ashes- * A branch or cross railroad is in operation as far as Walhalla ; but the single daily train runs at an hour not convenient for this expedition ; and Seneca City is probably the best starting-point. At all events, I obtained there an excellent mount for the trip.

Jan 1, 1879

By Thomas N. Walthier

If current trends continue, the shrunken world of exploration will keep on shrinking and the number of new mines will be insufficient to meet production requirements. Mineral shortages-not natural, but government induced-will then occur.

Jan 5, 1976

By A. W. Hesse

Twelve years ago, some coal-mine operators, mining engineers, oil and gas operators, Bureau of Mines engineers, geologists and state mine inspectors met in Pittsburgh, Pa. to discuss and solve if possible, the problems in connection with the drilling of oil and gas wells through or near coal mines and through the future coal reserves. Regulations were drafted and presented by O. P. Hood and A. G. Heggem of the Bureau of Mines.&apos; . There was considerable discussion of the various articles, practically all of which appear in Bulletin 65, but the interest aroused at that meeting was short lived. Practically none of the important coal-producing states gave the matter the consideration it should have received. Notwithstanding the marked progress in safety work, coal mines still have an unenviable reputation for mine explosions. Our mining laws have become stricter and the enforcement, especially in Pennsylvania, more rigid, but what good will come from a rigid enforcement of the mining laws if some source of danger exists all around the mines, over which the operators have no control ? It is hardly necessary to recite all the cases of natural-gas explosions published in Bulletin 65, but with some of them I am especially familiar. In 1912, while visiting the Miners&apos; Hospital, at Fairmont, W. Va., my attention was called to a patient swathed in in bandages so that no part of his face and hands were visible. He had not been told that his two sons, mere boys, had died of the burns they had received in the same accident—explosion due to natural gas leaking into a country mine at Peora, Harrison Co., W. Va.

Jan 1, 1925

By M. Safiuddin

Within the mining industry, open-pit mining has progressed to a point where a 200-yard walking dragline is as conceivable today as a 35-yard dragline was just a few years ago. This is possible due to the technological advances and efforts of the excavator manufacturers, and the manufacturers of electrical equipment have always stayed abreast with them in meeting their requirements and in making available their experience with the latest control techniques and hardware from various fields for application in the mining industry. An electrician in the coal mines of Pennsylvania who had not heard the word "thyristor" a few years ago now wonders how the old excavators with Rototrols® and magamps could ever work. The thyristors, transistors and operational amplifiers which were considered too fragile and delicate for a rugged and severe application like the mining industry, today constitute the brain of an excavator control taking commands from the operator and giving signals to the muscles of the excavator to move the bucket within a few seconds. A giant 200-yd bucket filled with overburden moves within seconds of the operator&apos;s command. Digging cycles for these excavators range from 40 to 60 sec depending on the swing angle. With these tremendous production capabilities of the excavators, the equipment failures and downtime become very expensive, and the loss of return on large capital investment for such machines becomes intolerable. Even though these failures and downtimes cannot be avoided completely, a good preventive maintenance program can help reduce them, thus increasing the machine availability. As we shall see below, the causes for breakdowns and failures of electrical equipment can be analyzed and a good preventive maintenance program can be drawn up to eliminate most of these failures.

Jan 9, 1967

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:&apos;,&apos; oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964