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By H. J. Stehli

Probably the earliest sinter from lead ore was made in the product sinter boxes attached to some hand reverberatory roasters. The ore was drawn from the roaster bed when dead roasted, and then by laborious effort fritted together by rabbling at a high temperature in the sinter box. This was not a true sinter, but was a great improvement over the dusty dead-roasted fine ores. The Huntington-Heberlein pots were the first real advance in the art, and produced some real sinter. They required that the sulphides be preroasted to 5 or 6 per cent sulphur, and the long cycle of operating and deep bed of material used in the pots fostered the formation of densely fused material and fines. This necessitated crushing of the densely fused cake and returning to the next charge large amounts of fines screened out. The Huntington-Heberlein pots made comparatively high lead losses because the deep bed and high internal temperature together favored the volatilization of lead. Lime (CaO) was added to the charges, and this addition constituted the patented feature of the Huntington-Heberlein process. Its sole function we now know was to act as an isolator of the sulphide particles, and any other substance—for instance, iron oxide—of equal fineness performed the same function. The Savelsberg process used limestone instead of burned lime, and in this there was a definite advantage. The converting of CaCO3, to CaO is a highly endothermic reaction, so the lime acted not only as an isolator of sulphide particles but absorbed excess heat and to some extent prevented premature fusion of the sulphides. The Carmichael-Bradford process used gypsum instead of limestone, and had the disadvantage of adding more sulphur to a charge from which it was desired to eliminate sulphur. Here again the gypsum served only as an infusible isolator of sulphide particles. The first Dwight-Lloyd apparatus to sinter lead ores commercially was installed at Perth Amboy in 1907. The fact that lime in any form was necessary to sintering was quickly disproved by making excellent sinter from Bunker Hill and Sullivan table concentrates, silica sand and iron oxide only.

Jan 1, 1937

By Ward W. Minkler

Since 1978, the titanium metals industry, throughout the non-socialist world, has experienced a period of growth and prosperity unparalleled since the late 1950s. Sponge producers, melters and mill product manufacturers have operated at capacity, record shipments have been attained, new producers have entered the industry and established producers have implemented expansion plans. However, there is now mounting evidence that the underlying elements which generated this vigorous surge have abated, at least temporarily. It now appears that in 1982, the industry will encounter overcapacity, excessive inventory accumulations and the probability of declining prices. Therefore, it does seem appropriate that we now take inventory of the present and future markets for titanium with the hope we can identify both near term opportunities as well as challenges the industry now faces. If we view the development of titanium markets as a function of time, they fit rather neatly into three sectors.

Jan 1, 1982

By C. W. Hill

FLUXES, in general, may be classified according to their use as soldering, foundry or casting, and metallurgical and the chemistry of their action follows quite closely this division. The term foundry or casting fluxes, as used here, refers to the substances added to molten metals, preparatory to casting into molds or ingots, with the object of removing small amounts of impurities that have been introduced in handling or melting the metal, which was placed in a fair state of purity by the previous refining or metallurgical processes. The sources of these impurities are the oxide coating on the surface of the ingots, material extracted or mechanically removed from the crucible or furnace wall, and those formed by the reaction of the molten metal with the heating gases or furnace atmosphere. As commonly used, the term fluxes is applied to such materials as ammonium chloride, zinc chloride, salt, borax, and boric oxide. A second class of materials, usually called deoxidizers, includes substances, such as metallic phosphides, sub-oxides, carbides, and bo-rides, that reduce the metallic oxides present in the metal. A third class includes various compounds that are molten and non-volatile at the temperature of the molten metal and are used primarily to protect the surface of the metal from the action of the furnace or exterior atmosphere; to this class belong such mixtures as lime and fluorspar, lime and soda ash, various minerals, etc. In some cases these protective layers may act in a manner similar to the metallurgical fluxes and dissolve or unite with the oxide impurities of the metal, but as generally employed this latter action is negligible since there is little opportunity for the coverings to come into contact with more than the surface of the metal, and hence they are without action on the body of the molten mass. The use of fluxes is the result of factory experience and tradition, but an extensive study has not been made of the chemical, and physical actions that occur or the effects of these actions on the properties of the metal. It would seem necessary in any successful study of metal fluxes

Jan 10, 1920

By W. B. Vietz, C. W. Hill, T. P. Thomas

FLUXES, in general, may be classified according to their use as soldering, foundry or casting, and metallurgical and the chemistry of their action follows quite closely this division. The term foundry or casting fluxes, as used here, refers to the substances added to molten metals, preparatory to casting into molds or ingots, with the object of removing small amounts of impurities that have been introduced in handling or melting the metal, which was placed in a fair state of purity by the previous refining or metallurgical processes. The sources of these impurities are the oxide coating on the surface of the ingots, material extracted or mechanically removed from the crucible or furnace wall, and those formed by the reaction of the molten metal with the heating gases or furnace atmosphere. As commonly used, the term fluxes is applied to such materials as ammonium chloride, zinc chloride, salt, borax, and boric oxide. A second class of materials, usually called deoxidizers, includes substances such as metallic phosphides, sub-oxides, carbides, and bo-rides, that reduce the metallic oxides present in the metal. A third class includes various compounds that arc molten and non-volatile at the temperature of the molten metal and are used primarily to protect the surface of the metal from the action of the furnace or exterior atmosphere; to this class belong such mixtures as lime and fluorspar, lime and soda ash, various minerals, etc. In some cases these protective layers may act in a manner similar to the metallurgical fluxes and dissolve or unite with the oxide impurities of the metal, but as generally employed this latter action is negligible since there is little opportunity for the coverings to come into contact with more than the surface of the metal, and hence they arc without action on the body of the molten mass. The use of fluxes is the result of factory experience and tradition, but an extensive study has not been made of the chemical and physical actions that occur or the effects of these actions on the properties of the metal. It would seem necessary in any successful study of metal fluxes to determine not only what impurities are present in metals melted under

Jan 1, 1921

By Clarence W. Balke

SMALL buttons of fused tantalum have been produced by arc fusion in a vacuum, by drawing an arc between sticks of pressed tantalum and a tantalum-faced water-cooled copper block. However, ingots of appreciable size can be produced only by the heat-treatment of bars pressed from powder. The following outline covering the production of finished bars of tantalum by the methods of powder metallurgy is also used for the production of columbium, taking into account the difference in the melting points of these two metals. PRESSING THE POWDER With possibly a few exceptions, a pressing operation is one of the essential steps in the practice of powder metallurgy. In fact, the author's experience with a number of high-melting-point metals and with numerous types of hard carbide compositions has led him to believe that this operation is often one of the most important in the entire process, and frequently one of the most difficult to carry out in a satisfactory manner. Defects due to improper pressing can readily lead to a defective finished product. It is the author's opinion that rarely is a bar or other article pressed from metal powder in such a way that all parts of the piece are uniformly pressed. The nearest approach to uniformity of pressing is possibly attained when the powder is contained in a flexible receptacle, such as rubber, and is pressed under a liquid by hydrostatic pressure. However, this method is not generally applicable. Hydraulic pressing in steel dies where one or two punches are forced into the die must usually be resorted to. As the pressure in such a die is built up, the powder begins to cling to the walls of the die with a tenacity dependent upon the nature of the powder, and this results in a bridging action, so that the layers of powder adjacent to the moving punch are pressed more heavily than those further removed in the mass. Frequently, as the pressure is carried higher, there may be a mass slippage of the powder upon itself, with the result that slip cracks are formed within the pressed

Jan 1, 1938

J. Lainson Wills, Ottawa, Can. (Communication to the Secretary) : The localities of the Quebec and Ontario apatite deposits, and the nature of their occurrence haye been often described in the Transactions and in other publications that are readily available, and I do not, therefore, intend to discuss the many details advanced in Mr. Small's paper beyond the following two points:

Jan 1, 1893

By Katherine Mather

This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. Results of the properties of these rocks on their performance as concrete aggregates are discussed.

Jan 10, 1953

THERE is probably no phase of basic open-hearth steelmaking that is more of an art and less of a science than mold and pouring practice. It varies widely from plant to plant; consequently it is obviously impossible to set down in detail in this chapter the many ramifications of practice that are now used. The discussion that follows therefore attempts only to give an outline of the more common methods, with examples sufficient to indicate some of the variations in procedure, and to emphasize a few of the many underlying problems that face the open-hearth operator at the pouring platform. MOLD DESIGN Ingot molds are hollow castings of considerable wall thickness. Despite this, non-uniformity in wall thickness should be strictly avoided to prevent the setting up of unnecessary stresses. Molds are cast in various forms, sizes, and shapes depending on the type of steel, and on whether the ingot is to be withdrawn from the mold or the mold from the ingot. The selection of ingot-mold material, which is usually cupola or blast-furnace iron containing approximately 3.5 per cent carbon, 1 per cent silicon, 0.9 per cent manganese, 0.2 per cent phosphorus, and 0.07 per cent sulphur, is governed by numerous considerations that affect mold life. (1) Factors in addition to wall thickness that should be given primary consideration at the foundry are casting skin, shrinkage stresses, and casting temperature. Factors in Mold Design. In use, mold thickness is of greatest importance, for it must be heavy enough to freeze the molten metal rising in the mold and to reduce the temperature of the steel below that of the melting point of cast iron to prevent the inner surface of the mold from melting, which would result in the welding of the ingot to the mold. The skin of an ingot, which solidities immediately upon contact with the relatively cold walls of the mold, must soon become thick enough to contract on the fluid mass and pull away slightly from the sides of the mold. The separation of the ingot from the mold depends entirely on the heat taken up by the mold from the steel.

Jan 1, 1944

By Thomas T. Read

EVERYONE engaged in the teaching of mining engineering will, I suppose, agree that the most difficult subject to teach is "Mining Methods." One primary difficulty is that the students taking the course have either had no previous experience in mining, or else they have had; either seeming to be somewhat of a drawback. The students who are unfamiliar with mines find it difficult to visualize underground conditions, as described and illustrated with sketches and maps, while those who have had underground experience seem to 'find it difficult to visualize anything much different from that which they have already seen. This reminds one of the remark about the Presbyterian doctrine of predestination, to the effect that "you are damned ,if you do; and damned if you don't."

Jan 1, 1930

By Clarence W. Balke

Small buttons of fused tantalum have been produced by are fusion in a vacuum, by drawing an arc between sticks of pressed tantalum and a tantalum-faced water-cooled copper block. However, ingots of appreciable size can be produced only by the heat-treatment of bars pressed from powder. The following outline covering the production of finished bars of tantalum by the methods of powder metallurgy is also used for the production of columbium, taking into account the difference in the melting points of these two metals. Pressing the Powder With possibly a few exceptions, a pressing operation is one of the essential steps in the practice of powder metallurgy. In fact, the author's experience with a number of high-melting-point metals and with numerous types of hard carbide compositions has led him to believe that this operation is often one of the most important in the entire process, and frequently one of the most difficult to carry out in a satisfactory manner. Defects due to improper pressing can readily lead to a defective finished product. It is the author's opinion that rarely is a bar or other article pressed from metal powder in such a way that all parts of the piece are uniformly pressed. The nearest approach to uniformity of pressing is possibly attained when the powder is contained in a flexible receptacle, such as rubber, and is pressed under a liquid by hydrostatic pressure. However, this method is not generally applicable. Hydraulic pressing in steel dies where one or two punches are forced into the die must usually be resorted to. As the pressure in such a die is built up, the powder begins to cling to the walls of the die with a tenacity dependent upon the nature of the powder, and this results in a bridging action, so that the layers of powder adjacent to the moving punch are pressed more heavily than those further removed in the mass. Frequently, as the pressure is carried higher, there may be a mass slippage of the powder upon itself, with the result that slip cracks are formed within the pressed

Jan 1, 1938

By Clarence W. Balke

Small buttons of fused tantalum have been produced by are fusion in a vacuum, by drawing an arc between sticks of pressed tantalum and a tantalum-faced water-cooled copper block. However, ingots of appreciable size can be produced only by the heat-treatment of bars pressed from powder. The following outline covering the production of finished bars of tantalum by the methods of powder metallurgy is also used for the production of columbium, taking into account the difference in the melting points of these two metals. Pressing the Powder With possibly a few exceptions, a pressing operation is one of the essential steps in the practice of powder metallurgy. In fact, the author's experience with a number of high-melting-point metals and with numerous types of hard carbide compositions has led him to believe that this operation is often one of the most important in the entire process, and frequently one of the most difficult to carry out in a satisfactory manner. Defects due to improper pressing can readily lead to a defective finished product. It is the author's opinion that rarely is a bar or other article pressed from metal powder in such a way that all parts of the piece are uniformly pressed. The nearest approach to uniformity of pressing is possibly attained when the powder is contained in a flexible receptacle, such as rubber, and is pressed under a liquid by hydrostatic pressure. However, this method is not generally applicable. Hydraulic pressing in steel dies where one or two punches are forced into the die must usually be resorted to. As the pressure in such a die is built up, the powder begins to cling to the walls of the die with a tenacity dependent upon the nature of the powder, and this results in a bridging action, so that the layers of powder adjacent to the moving punch are pressed more heavily than those further removed in the mass. Frequently, as the pressure is carried higher, there may be a mass slippage of the powder upon itself, with the result that slip cracks are formed within the pressed

Jan 1, 1938

By Wilson Blake

Rock deformation and failure taking place around underground openings is usually both accompanied and preceded by the phenomena of rock noise or microseismic activity. These small-scale releases of seismic and acoustic energy can be detected with special geophysical monitoring equipment. Use of this equipment allows one to look inside a rock mass to determine how an opening is behaving under the applied loading system. Microseismic equipment and monitoring techniques are briefly reviewed, and use of the microseismic method as an engineering tool in monitoring rock structure stability is illustrated by case histories. Examples cited range from evaluating roof stability using single-channel portable equipment, to rock burst monitoring using sophisticated computer controlled, multichannel monitoring systems.

Jan 1, 1983

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-', a lo-'-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10' cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell's law that where = critical angle, n - index of refraction of air, n' - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,' and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert's law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

By William L. Fink, H. R. Freche

The constitution of the aluminum-cobalt alloys has been the subject of relatively few investigations. Brunckl analyzed the residue which remained after treating the 17 per cent cobalt alloy with dilute hydrochloric acid. The results of the analyses indicated the existence of a compound Co3Al13. Guillet2 published a liquidus for the aluminum-cobalt system which contained two maxima corresponding to CoA16 and CoAl2 and two eutectic points at 30 and 74 per cent Co. The most extensive investigation of the system was carried out by Gwyer13 whose results are summarized in Fig. 1. It will be noted that at the aluminum end there is a suppressed eutectic at 644' C. By extrapolation of the duration of the eutectic arrest to zero, the composition of the compound was placed at Co3Al13. Another thermal arrest was noted at 550" C., which Gwyer attributed to a peritectic reaction. The present investigation of the aluminum end of the aluminum-cobalt system is the eleventh of a series dealing with the constitution of aluminum-rich alloys prepared from electrolytically refined a1uminum.l Preparation of Alloys.—The alloys used in this work were all prepared from electrolytically refined aluminum, the analysis of which is shown in Table 1. In preparing some of the alloys, metallic cobalt (98 to 99 per cent) was used either directly or in the form of an intermediate alloy, the composition of which is given in Table 1. In order to obtain alloys of higher purity, cobalt was introduced into some of the alloys by means of chemically pure cobaltous chloride which was readily reduced by the aluminum. A small electric furnace with nickel-chromium heating elements was used in the preparation of the alloys. Chemical Analysis.—An analysis sample from each melt was chill-cast in the form of a plate 3/16 in. thick. In all cases the casting temperature was well above the liquidus. Cobalt was determined electrolytically in all alloys containing more than 0.05 per cent cobalt and by the nitroso-

Jan 1, 1932

FREderick H. Davis, Electrical Engineer of the Westinghouse Electric and Manufacturing Co., in charge of the plant at Bodie, Cal. (communication to the Secretary): I beg to offer, to complete the information conveyed in Mr. Leggett's paper, the following report of tests of the electrical efficiency of the power-transmission he has described:

Jan 1, 1895

By G. M. Lee

SEVERAL improvements have been made in Granby smelting practice since the company abandoned the direct smelting of raw ore in the blast furnaces in June, 1927, in favor of sintered concentrate. These improvements have been made in several fields, but the most novel and outstanding change was the development of a process of concentrating most of the gold, and a somewhat smaller fraction of the silver present, in a small portion of the blister copper produced. The practice of making "copper bottoms" is usually associated with the reverberatory smelting of copper ores containing high percentages of impurities, or of copper matte high in precious metals. It has for its object, in the one case, the production of a major part of the copper relatively free from impurities and, in the other case, the production of a small per¬centage of the copper carrying the major part of the precious metals. Although the blister copper produced at the Anyox plant of the Granby company is remarkably free from deleterious impurities and normally contains no great amount of precious metals, certain economic considerations made it advisable to concentrate the existing precious metals into a relatively small percentage of the blister copper produced. The process devised took advantage of principles and reactions of the usual bottoms processes, but was carried out in the converters instead of in a reverberatory furnace.

Jan 1, 1935

By C. E. Wood, E. P. Barrett, T. L. Joseph

The United States Bureau of Mines has been studying the blastfurnace process for about ten years. An experimental furnace was developed by the Burcau in cooperation with the Minnesota School of Mines Experiment Station, University of Minnesota. Many data have been obtained and published.' Royster, Joseph and Kinney §(48) found that the particle size of ore had an important effect upon the blast-furnace process. Kinne(28) stated: Economy in blast-furnace practice depends largely upon efficient gas-solid contact in the shaft of the furnace. If efficient work is not done in the shaft, the hearth and bosh will not function properly. A condition may be readily imagined where the particles of ore in the shaft are so large that the time entailed in the descent of these materials into the bosh is not sufficient to permit proper reduction and preparation prior to the time the ore enters the bosh of the furnace. Another condition may be pictured where the density of theatock column and the flow of stock is such that the ore will take one course and the gas another. Both of these examples will result in insufficient contact between the gas and the ore. Unreduced ore will reach the hearth, and the gas which has not been efficiently oxidized will reach the stock line. The result is the use of an excess of carbon in the smelting process. It is obvious that fine ore particles occurring in the ore as charged, or formed in the furnace due to heat and mechanical action, place a definite limitation upon the efficiency of the operation. There is also an economic loss of fine material as dust. Effect of Size of Material Kinney reported (p. 83(29)) the reduction of iron oxides between planes at three furnaces as given in Table 1. The Chicago furnace was operated on Lake ores. Distribution of gas was not good and much of the charge passed into the hearth before the iron oxide was reduced. The Holt furnace was operated on coarse ore. Distribution of gas was fairly uni-

Jan 1, 1930

In 1962, minerals beneficiation showed definite signs of coming out of the doldrums into which it has drifted after the uranium boom. Demand by steelmakers for high-grade iron pellets has created the need for concentrating plants to upgrade specular hematite by spiral concentration or flotation and magnetites by magnetic means and flotation. According to a paper given at the AMC annual meeting by C. S. Arms of Pickands Mather, "the shipment of pellets, started in the mid-1950's, has increased to 17.6 million tons in 1961 from North American operations. Many plants already underway will raise this production to about 42 million tons by 1965. This will be a very sizeable percentage of the total iron ore production contemplated by that date." Iron ore concentration methods are gradually raising the assay of pellets into the 65 to 69% Fe range and lowering silica to the 4 to 7% range. Quebec Cartier's Lac Jeannine concentrator went into operation in late 1961 and all grinding units were running by 1962. The Iron Ore Co. of Canada's new Carol Lake plant was started in mid-1962.

Jan 2, 1963

By A. B. Parsons

AN often repeated criticism of the profession of engineering is that it is as a whole it lacks solidarity. organization, co-ordination, and leadership. Significantly, the critic, are all engineers. Other members of the body politic either do not know about the absence of organization or they do not care. If engineers have no organization they have a plethora of organizations. There exist in the United State, today some 350 societies. institutes. clubs, associations, and councils of engineers and engineering technologists and this number excludes several hundred local chapters of national societies. trade associations, and local engineers' clubs of purely social character- Successful engineers must be proficient in analyzing, planning, and co-ordinating. but it is generally admitted that for their profession as a whole their success in this respect has been indifferent.

Jan 1, 1943

By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970