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By R. L. Tobie

Handling and storing ore at transfer points underground are encountered frequently. An ideal solution to these troubles is probably still to be found, but at the Mather mine "B" shaft a method incorporating scraping trenches has been developed giving better service, from the standpoint of safety and simplicity, than obtained from other schemes. When shaft pockets are used for storage, the size of the ground opening required to assure capacity is often prohibitive, and shaft depth below the last level can become excessive, particularly if a crushing station is used. Also, if the material being handled contains large amounts of wet fines, it is difficult, if not impossible, to hold the material with regular chute gates. In order to remedy these problems Cleveland-Cliffs' Mather "B" has utilized three types of trenches. Types I and I1 are now in service and the third is under construction.

Jan 4, 1955

By Joseph Jensen

MANY fields have been zoned by nature with shales and intermediate waters between oil zones. Limitations thus imposed have been the basis on which the field was developed. In contrast thereto, in the Ventura Avenue Field, nature proved more generous. Always expecting to find such similar limitations, operators drilled deeper and deeper into the oil zone without finding any distinctive shale bodies other that the Gosnell shale and only one intermediate water, which became the point below which the final water shut-off of each well was made. Thus, on top of the structure, about 3300 ft. of oil-bearing zone has been penetrated below this intermediate w9ter-a distance of 4000 ft. below the Gosnell shale. At first it seemed that the greater the penetration in the zone, the better the well. The error of this assumption became evident

Jan 1, 1930

By GEO M. FOWLER

AN appraisal of the activities of the mining geologists during 1936 clearly indicates the ever in- creasing utilization of geology in the search for ore. Few men with geo- logic training are idle at present; this is particularly true regarding recent graduates. Many have accepted employment in distant fields, such as the Philippines and South America, and greatly increased mineral production from these places reflects their activities. In North America, regions of intense mineralization formerly important are being restudied in greater de- tail and with better understanding; as a result, new mineral wealth is being found in many such districts. Much is being done by private companies and individuals, and it is to be hoped that mining companies will increasingly make available the purely scientific results of such studies by permitting their geologists to publish. On such generosity to a large extent will future advances in ore finding depend.

Jan 1, 1937

By E. W. Rouse

THE year 1936 has seen rehabilitation of many plants which had been closed or severely curtailed. The Steptoe smelter of the Nevada Consolidated Copper Co. has been transformed by a rearrangement of the flow of material and utilization of mechanical handling to a maximum. The Phelps Dodge Corp. reports the construction of newer and better reverberatories at the Copper Queen smelter, and of particular interest, a single high-pressure waste-heat boiler placed directly over the uptake. There has also been a complete reconstruction of the smelter at the Laurel Hill plant of the Nichols Copper Co.

Jan 1, 1937

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By Peter N. Blakey, Thiann R. Yu, Douglas O. Tansey

A flexible, efficient, and relatively low-cost drilling and blasting operation has evolved at Texasgulf Canada, Ltd.'s Kidd Creek underground mine. Located 32 km (20 miles) north of historic Timmins, Ontario, the underground operation utilizes a sublevel open stoping method developed with large-diameter blastholes. Over the years, Kidd Creek engineers have experimented with various drill-and-blast techniques, leading to the present-day practice. Continuing work is being conducted to further mechanize the blasting operation.

Jan 6, 1976

By Scott Turner

GOLD AND SILVER, the monetary metals, have presented in the last year a striking contrast; gold has experienced unusual prosperity, while silver has been depressed more severely than ever before. Gold mining has been hailed as the only basic industry that is able to thrive on depression; the new gold produced is thought by many to be the most important material for the reconstruction of prosperity. Silver production, meanwhile, has been sinking to its level of 40 years ago, and its price to a level never before recorded. These factors have reduced the value of silver produced in 1932 to about the value of the average annual production more than a century ago, that of the decade 1801-1810. No other major commodity in world trade appears to have suffered a greater decline during the present depression.

Jan 1, 1933

By FREDERICK MCAKCCOY

THE production of tin from Mexico has never reached the point of being considered a national industry, but the distribution of tin ores is so widespread that there are possibilities that one day it may become of importance. Of the twenty-seven states of the Republic, tin claims have been taken up in sixteen. In all there had been taken up to the end of 1926, two hundred and twenty-five claims, of a total area of about 7400 acres. The first historical mention of tin in the Americas is found in a letter of Cortez to the Emperor, Charles the Fifth, of Spain, which is as follows: Speaking of his manufacture of some small cannon, he says: "For these reasons I took considerable pains to get copper from some provinces of this country, and bought it at a high price in order to get it quicker.

Jan 1, 1929

By R. J. Colony

MINING geology does not lend itself - very readily to a review embracing "improvements in methods," as perhaps do shop practices or laboratory procedures. The "methods" used in mining geology are simply the application of geology to mining; winning the ore, the handling of material, mechanical appliances, all belong strictly to mining proper, and have no place in a review of geology as applied to mining. A comprehensive review would necessarily cover a .very broad field, which could be subdivided into many -parts. Only a few of these can be discussed here. .Those that have been suggested to the chairman indude :

Jan 1, 1930

By ROBERT E. HARDWICKE

THE QUESTION of whether the production of oil should be limited to market demand has been constantly discussed during the last two years. Oil men, legislatures and courts have reached highly conflicting conclusions. Opponents of limitation to market demand assert that it is a scheme of the big purchasing companies to fix prices and to create a monopoly. Proponents, on the other hand, declare that such a limitation is necessary to prevent physical waste and that the effect on prices is merely incidental. A brief review of market demand legislation will disclose the confusion existing. The laws of Oklahoma,' prohibiting waste of oil and gas, specifically' authorize limitation to market demand as a method of preventink such waste. These laws and the proration orders based thereon have been upheld by the Supreme Court of Oklahoma, by several three-judge Federal District Courts, and by the Supreme Court of the United States.' Kansas has a similar law3 but no case has been found which discusses its validity. About a year ago the California Legislature passed a comprehensive conservation act, generally known as the Sharkey Bill giving authority to restrict production to an amount representing current requirements for use, taking into consideration oil and products in storage. This may be considered as equivalent to limitation to market demand. The Act was defeated upon referendum vote after a hard fought campaign in which it was charged that the Act would result in destruction of the independent operators.

Jan 1, 1932

By J. F. Shirley, H. K. Burke

In January, 1964, three years of laboratory and pilot plant test work reached its culmination. The San Manuel Div. of the Magma Copper Co. switched its molybdenite extraction circuit from the sodium hypochlorite-ferrocyanide process to the new process described in this paper. The San Manuel Div. Concentrator of the Magma Copper Co. is located near San Manuel, Ariz., approximately 45 miles northeast of Tucson. The concentrator treats approximately 35,000 tons of ore per day containing about 0.85% copper and 0.025% molybdenite. The San Manuel ore body is a disseminated copper deposit in quartz monzonite and quartz monzonite porphyry. The primary copper mineral is chalcopyrite; minor amounts of chalcocite, bornite and covellite are also present in varying degrees. Pyrite makes up somewhat more than half the sulfide content of the rock. The molybdenite is nearly always found on fracture faces or associated with quartz veinlets.' On January 9, 1964, the sodium hypochlorite-ferrocyanide process that had been used for molybdenite recovery was replaced by the following process: 1) A conditioning step with hydrogen peroxide, sulfuric acid, sodium cyanide and zinc sulfate. 2) A two stage rougher flotation step with stove oil and sodium ferrocyanide. 3) One cleaning step with sodium ferrocyanide. 4) One cleaning step with sodium hypochlorite and potassium ferricyanide. 5) Four cleaning steps with an anti-foam Exfoam 636 and potassium ferricyanide. COPPER CONCENTRATOR Since molybdenite recovery is closely allied with previous steps in the operation, the copper concentrator will be briefly described first. The ore is ground to approximately 5% plus 65-mesh and 65% minus 200-mesh in a two-step grinding circuit consisting of rod mills in open circuit and ball mills in closed circuit with rake classifiers. A straight forward rougher circuit producing only one concentrate is used. The rougher concentrate is combined with the discharge from the regrind ball mills and is then cycloned, with the overflow going directly to the cleaner circuit and the underflow going to the regrind mills. The feed to the cleaner circuit is approximately 90% to 94% minus 325 mesh. The cleaner circuit consists of two stages in which the tailing from the final cleaner stage is returned to the primary cleaner and the primary cleaner tailing is returned to the rod mill discharge at the head of the circuit. Approximately 0.013 lb of the allyl ester of amyl xanthate (S-3302) per ton of ore is added to the rod mills and approximately 0.006 lb of sodium isopropyl xanthate (2-11) per ton of ore is stage added down the rougher banks. The frother used is methyl iso-butyl carbinol (MIBC) and it is added at various points in the grinding and the rougher flotation circuits. Lime is added to the ball mills and/or to the rod mills to maintain the desired pH in the rougher flotation. The rougher flotation has been operated at various pH levels between 10.5 and 11.5. Fuel oil is added in the regrind mills at a loading of approximately 0.01 lb per ton of ore. Factors Which Directly Affect Molybdenite Recovery: It has been found at San Manuel that, to obtain maximum molybdenite recovery, an oily type flotation collector must be added in the grinding circuit. When molybdenite is crystallized in the characteristic platy form, which appears to be the case almost all of the time at San Manuel, its surface has a greater tendency to adhere to oils than water. 2 Of the several oily type collectors available on the market, the allyl ester of amyl xanthate seems to be the best molybdenite promoter. The floatability of San Manuel's molybdenite does not appear to be affected, at least up to a pH of 11.5, by lime. It has been reported that at several plant operations high lime alkaline circuits have adversely affected the molybdenite recovery.3,4 It has been found through microscopic studies that the bulk of the chalcopyrite will float before the molybdenite in both the rougher and cleaner circuits. It is necessary to add fuel oil to the regrind mills to enhance the

Jan 1, 1965

By H. H. Moss

OXYACETYLENE .cutting has experienced rapid development in the last few years and greater advances and expansion and broader application may be expected in the immediate future. Marked changes in cutting practice may be expected as a result of the advances in metallurgical science that have produced special alloy steels with properties requiring different cutting techniques than for ordinary low-carbon steels. Much current attention is being directed to those problems of modified cutting practices. Cutting has thus ceased to be merely a shaping problem. It is rapidly coming to have a predominantly metallurgical aspect. The problem is no longer how to cut a given shape, but how to cut a given steel. The answer

Jan 1, 1936

By AIME AIME

TWO days of solid discussion, with barely time out for meals, characterized the Tulsa meeting of the Petroleum Division. It was preeminently an earnest gathering devoted to technical matters. Sessions were held in the Crystal room of the Mayo Hotel with luncheon served each day in the back of the same room so that talk of methods, while slightly less formal, extended right through the lunch hour. Thursday evening the Committee did provide a little relaxation in an informal dinner at the Tulsa Club where, after a brief musical program and an amusing skit by the local Herman the Great, brief addresses in non-technical vein were made by President Farish and Vice-president Rice of the Humble Company, Henry L. Doherty of Cities Service, Secretary. Bain of the Institute, and others. The presence of leading executives of a number of the oil companies at the dinner and the sessions, and the cordial approval they expressed of the work of the Division were especially gratifying. The total registration was 215 with 100 at the dinner and 70-to 80 lunching together each day.

Jan 1, 1930

By G. C. Wallick, W. R. Foster, J. G. Savins

Inasmuch as the differentiation and integration methods represent different modes of rheological analyses, a dual scheme of analysis using both methods should lead to a generalized method of data analysis. A dual differentiation-integmtion method of analysis is applied here to the Poiseuille flow of a variety of ideal Generalized Newtonian and viscoplastic models. Using machine-processing techniques, the result is a spectrum of response patterns which are expressed in terms of certain derivative functions. It is shown that these characteristic functions form the basis of a highly-sensitive analytic technique for optimizing the selection of the most appropriate functional relationship between shear rate and shearing stress. INTRODUCTION In the first paper of this series, Savins, Wallick and Foster1 presented an historical review of the salient features of the differentiation method of rheological analysis in Poiseuille flow, and also indicated how the method could be applied to problems involving plane Poiseuille flow. It was shown that the differentiation and integration methods, although basically not incompatible, do represent different modes of rheological analysis. This suggests that valuable background information regarding the probable response characteristics of real data obtained with the differentiation method can be obtained from an integration method-differentiation method analysis of the response of a variety of ideal rheological models. The present paper describes how this dual method of analysis has been applied to suites of idealized models representing a wide variety of Generalized Newtonian and viscoplastic behavior which have received attention at various places in the literature.

By E. W. Parker

THE anthracite region, from which there is produced annually about 80,000,000 tons, or approximately 15 per cent. of the total coal supply of the United States, has a combined area of a little less than 500 sq. mi. The total area occupied by the bituminous fields (including the sub-bituminous and lignite fields) is in the neighborhood of 400,000 sq. mi., so that 15 per cent. of the total output comes from this small area of only a little more than 0.1 per cent. of the coal-producing territory. of the United States. The productive anthracite area is divided into a series of basins or troughs, roughly parallel, extending. in a northeast-southwest direction through the. Counties

Jan 1, 1921

By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n', and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.',~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1'2'5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen' and others.2'9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.'' Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969

By J. C. Savins, G. C. Wallick, W. R. Foster

The dual differentiation-integration method of rbeological analysis is applied to Couette flow. Using machine processing techniques, a spectrum of characteristic derivative functions for a variety of ideal Generalized Newtonian and viscoplastic models has been developed; As for the case of Poiseuille flow the functions for Generalized Newtonian models as a class are strikingly different from the corresponding functions for the class of viscoplastic models. It is shown that this dual scheme of analysis is a highly sensitive analytic method for dotermining the applicable range if a rbeoloaical model. The unique characteristics of this function in the case of viscoplastics may lead to a more precise detection and evaluation of the yield point or yield stress in these materials. INTRODUCTION It has been shown 1,2 that the dual differentiation-integration method of analysis is a discriminating and flexible method for interpreting flow behavior and determining the applicable range of a particular model from Poiseuille flow experiments. In the preceding paper3 the basic equations governing the Couette flow experiment were reviewed and the significance of changes in boundary conditions on data analysis in the case of the viscoplaaic discussed. In this paper the dual method of analysis is applied to Couette flow using the suites of rheological models considered previously.

By Paul M. Tyler

ROUGHLY one-half the value of mineral products at mines or quarries must be spent for wages. In view of the steady increase in hourly wages that continued for several decades prior to the onslaught of the recent depression, it is perhaps surprising to discover that labor's share of the gross proceeds of the mining and quarrying industries of the United States declined to 46.8 per cent in 1929, compared with 52.2 per cent in 1919 and 53.2 per cent in 1909. The actual percentages vary in different branches of the industry and in different localities but the downward trend is unmistakable. For the period 1909 to 1919 it was quite marked in every industry and from 1919 to 1929 it was apparent in all but six: namely, gold and silver lode mining, placer gold mining, crude gypsum production, marble quarrying, asbestos production, and fluorspar Tninino mining

Jan 1, 1933

By N. Parlee, V. C. Kashyap

The solubilities of nitrogen in liquid iron and liquid Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys were measured by the Sieverts method. Measurements were made at 1600° to 1800°C on binary alloys up to 20 pet Ni, 10 pet V, 10 pet Mo; and on ternary alloys containing 0 to 3 pet V with 0 to 5 pet Mo. The results on liquid iron confirm that Sieverts' law is obeyed in the range 50 to 750 mm pressure. The measured solubilities and their temperature coefficients are in general agreement with other modern authors. The logarithms of the activity coefficients of nitrogen in the binaries are approximately linear functions of the pet of alloying element. A method suggested by Wagner, Chipman, and others for predicting gas solubilities in complex alloys from solubility data on binaries was applied to the Fe-Mo-V alloys. Reasonably good agreement was obtained between calculated and experimental solubilities. NITROGEN'S solubility in liquid iron has been studied by a number of investigators. It is reasonably well established that the solubility of nitrogen follows Sieverts' law at least up to 1 atm partial pressure and that the solubility increases gradually with temperature. The solubility of nitrogen in Fe-X binary liquid systems has been investigated in only a few cases. Only the systems Fe-Cr,3-5, 7 Fe-V,3 Fe-Mn,3, 5 Fe-Ni,3, 5 Fe-Si,B, H Fe-C, L, H and Fe-P4 appear to have received any study. The only work on liquid Fe-V was done by Brick and Creevy.3 This was limited to 13.5 pet and 26.5 pet V, but no exact temperatures were recorded. No work whatsoever appears to have been done on liquid Fe-Mo alloys and even work on Fe-Ni alloys is rather scant. The work on liquid ternary systems is still more limited, and the only publication available appears to be that of Wentrup and Reif,7 who studied the Fe-Cr-Mn and Fe-Cr-Ni alloys. Rassbach, Saunders, and Harbrecht17 have reported work on the solubility of nitrogen in stainless steel but this was not a systematic study of any particular system. Commercial alloys usually contain several alloying elements. Thus, it often becomes important to be able to predict the nitrogen solubility in systems containing two or more added elements without the necessity of making measurements. Wagner,14 Chipman," Darken and Gurry," and Morris and Buehl 14 have suggested means by which this may be accomplished, and Langenberg14 has recently applied one of these methods to nitrogen solubility in complex liquid alloys. This paper reports the results of nitrogen solubility determinations on Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys and compares calculated and experimental solubilities in the ternary alloy. Attempted measurements on Fe-Cr alloys were not successful by the experimental method employed. Experimental Method The general method of solubility measurement was that of Sieverts.' The apparatus and procedure were essentially the same as used by Liang, Bever, and Floe."' The equipment consisted of a small vacuum furnace heated by a 6 kw induction unit, gas measuring apparatus, and a gas purification train. The crucibles used were Norton Alundum with alumina sand around them for insulation. The crucibles were charged with 100 to 200 g of material, about 180 g or nearly filling the crucible being found most satisfactory. Hot volumes were determined with argon and ranged from 95 to 130 cu cm (stp). Temperature measurements were made with a Leeds and Northrup optical pyrometer which was calibrated periodically against the melting point of iron in the same apparatus."-'* Good quality nitrogen, hydrogen, and argon gases were further purified and dried in standard purification trains. The sources of the high purity iron and other alloying elements used were as follows:

Jan 1, 1959

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:',' 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