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By Edward Keller

ALTHOUGH the subject matter contained in this paper is presented under a new title, its writing was induced by the work of S. Skowronski and K. W. McComas.1 A discussion of the latter is here combined with the presentation of new and independent data. The physical constants quoted by the authors of that paper, such as melting and boiling points, as also the chemical reactions of the substances involved, are so well established that the numerous confirmatory experiments and their application to metallurgical conditions leave little or no room for criticisms. On the contrary, they will greatly aid to dispel any lingering skepticism as to possible considerable losses of copper accruing when the metal is melted in the presence of its own and, probably, other chlorides and when no provision is made for the recovery of volatile products. Exception may be taken, to some degree, to that part of the work under the caption Melting Drillings of Copper Mixed With Sodium Chloride. These experiments should have been extended in order to make the implied reactions clear and the results convincing. The latter are stated to be, "that when sodium chloride is present above certain minimum quantity relative to copper some of it is found to volatilize in the melt while another part reacts with the metallic copper to produce the volatile cuprous chloride, and that When smaller quantities of sodium chloride are present the reaction is complete and all chlorine is found to have volatilized as cuprous chloride." Metallic copper and sodium chloride are mentioned as the sole reagents in this chemical process, acting, according to the authors, in a neutral atmosphere of carbon dioxide. The chemist, quite naturally, will inquire into the formula according to which that reaction takes place and find that it would present itself as follows: 2Cu + 2NaC1 = 2Na + Cu2Cl2 It would appear that the truth of this formula will be challenged and a more rational explanation of the reaction sought. Apparently, carbon dioxide is neutral relative to metallic copper in its molten state; whether it remains neutral in the presence of sodium chloride is quite another question. Does it not at that high temperature become an oxidizer and do not the conditions of the reaction change to those expressed in the following formula? 2Cu + 2NaCl + 2002 = Na2CO3 + CO + Cu2Cl2

Jan 9, 1919

By AIME AIME

A STUDY of subsidence and ground movement in the copper and iron mines of the upper peninsula of Michigan has been made by W. R. Crane of the United States Bureau of Mines and published as Bulletin 295 of 66 pages and 49 illustrations. As a result of subsidence, the country adjacent to the mines and over- lying the mine workings in this district is often broken to such an extent as to affect its value; mine shafts and development openings are occasionally so damaged as to be rendered useless, and water can enter the workings through fractures and cave-ins. The problem is more serious in the iron-mining districts, where villages and towns not owned by the operating companies have grown up around mining operations.

Jan 1, 1929

By F. Z. Schellenberg

Systematic exploitation in the Pittsburg coal-seam on a large scale is simple where the boundaries of the property do not interfere by forcing drainage-, ventilation-, and transport-lines of entries to be run to particular confined fronts. A prime condition governing development is the natural direction of the seam's perpendicular cleavage-planes, giving long lines of smooth faces near together and parallel, bearing about 65' to the left of the meridian and therefore crossing the basins. The gradients of dip into the basins change from 10 per cent. at the east rim to practical flatness northwestward across the great coal-fields, a hundred miles wide; the dip being halved in rate at each successive crossing-over of an anticlinal crest. Elevations above sea-level on this transverse section, in scope of present development, differ by 1,000 ft. between low trough and high outcrop. Local irregularities of dip are found, but the main feature to be recognized is the pitch of the basins—the general rise northeastward at 20 ft. per mile, from 100 ft. below sea-level at the low point near the SW. corner of Pennsylvania to 1,500 ft. and more above tide, and the appearance then, at the surface, of the lower coal-seams carried in the next deeper-lying thousand feet of rock-measures; below which series come the oil- and gas-sands of Oliphant's charted column of strata, reaching down altogether 3,000 ft. below the Pittsburg coal-seam. Because of the general regularity of occurrence of the coal-seam, the mine-map depicting the courses of economic operation to be undertaken and the steps in controlled exhaustion, need be but a projection of two dimensions on the horizontal plane of space, and this for the most part composed of natural, almost unbroken lines, on the face and on the end of the coal, co-ordinating rectangularly.

Jan 1, 1911

By R. R. Sayers

TWO serious hazards from coal dust confront the bituminous-coal miner- -a physical or safety hazard and a physiological or health hazard. The first threatens the miner with loss of life from coal-dint explosions, and the second with loss of health and earning capacity from inhaling large quantities of the dust. Studies by the Bureau of Mines have shown that coal dust, except some grades of anthracite dust, is capable of initiating an explosion when no explosive gas is present and that its property of extending or propagating an explosion has been responsible for nearly all the widespread explosions that have occurred in bituminous mines in the United States in the present century. For years many mining people believed that low-volatile coal dust was not explosive but not only is it explosive but if the source of ignition is intense, it is as explosive as the dust of many high-volatile coals because the war is creating increased pressure for greater coal production and because of the trend toward greater mechanization in mines, explosion and health hazards from coal dust are likely !n increase considerably.

Jan 1, 1943

By Rossiter W. Raymond

In the course of this address, President Raymond referred to the law, said to have been discovered at the French works of Terrenoire, that the amount of phosphorus may be increased without injury to steel, if the amount of carbon be proportionately decreased. The works named have been for more than a year, it is said, manufacturing in the open hearth, by the Martin process, steel rails containing as high as 0.35 per cent. of phosphorus, with about 0.15 per cent. of carbon, which were not found inferior to Bessemer rails. It is not claimed by the manager of the works that phosphorus is an ingredient to be preferred, or purposely introduced; but only that materials containing it (such as old iron rails, etc.), can be succesfully employed. Other parties have apparently a higher opinion still of the new manipulation, and are prepared to claim for " phosphorus steel" superior qualities. Mr. I. Lowthian Bell alluded to the subject in his recent address as President of the British Iron and Steel Institute, but without expressing a positive opinion. After pointing out that the commercial value of the process turned on the cheap manufacture of ferro-manganese, by means of which only could the necessary amount of manganese be introduced into the Martin bath, without increasing its contents of carbon, Mr. Raymond proceeded to say that the principle alleged to have been discovered at Terrenoire was already known years ago, in this country, at least. Not only had steel been manufactured here, containing high percentages of phosphorus, coupled with low percentages of carbon, and suitable for use in rails, boiler-plates, etc., but the reason of its surprising qualities had been distinctly surmised, if not widely proclaimed. The following analyses and extracts from private letters prove these assertions. Some of them assert a similar principle in .the case of wrought iron; but the analyses, and the remarks based upon them, have reference solely to the steel manufactured under the superintendence of Mr. Slade, at the works of the New Jersey Steel and Iron Company in Trenton.

IN general in making such powders, all kinds of gravel, tuff, washed river silt, and similar earths whose grain is fine and lean by nature are good for this operation of casting, either by themselves or in mixture because they are disposed to receive the metals well on account of a certain dryness which they possess. Many kinds are also compounded by means of art. Of these, I shall proceed to tell of all those that experience [119] has taught me to recognize as good. But first I desire that we return to speak of the natural ones because they are real earths and can always be had wherever one may be, and in the necessary quantity. They please me greatly because they are easy to reduce on account of their disposition. A loam is made from these and mixed by beating with wool-cloth cut- tings, spent wash ashes, and horse dung. This is made into cakes and dried. These are then put to bake in a furnace or in some other way and, in fact, are baked very well. Then it is pounded and sifted with a fine sieve, or it is ground in a potter's color mill, or by hand on a porphyry with water, to the fineness that the craftsman desires, or as fine as he can make it. When it has been ground it is again drained free from water and dried out with fire. Then as much magistery of salt is taken as will moisten it. It is dried and pounded again and passed through a sieve. When it has been made as desired in this way it is moistened again before use with water, urine, or vinegar just enough so that it holds together when it is squeezed in the fist. Then, when it has been brought to this point, it is moulded as you will hear. Powders are also made of crushed brick, tripoli, vine ashes, tiles, and glazed drainpipes, or burned emery, calcined tin, straw, and of burned paper and horse dung as well as of young ram's-horn ashes and many other things. The goodness of all these depends on three things; namely, on receiving the metal well, on being so fine as to be almost impalpable, and on their being made .with a magistery that renders them hard and strong when they are dry. In addition to these powders I have used another when I needed it, and it has succeeded well every time I made it. To make this. I have taken I two parts of pumice and one of iron scale and ground them on the por-

Jan 1, 1942

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By F. Z. Schellenberg

(Pittsburg Meeting, March, 1910.) SYSTEMATIC exploitation in the Pittsburg coal-seam on a large scale is simple where the boundaries of the property do not interfere by forcing drainage-, ventilation-, and transport-lines of entries to be run to particular confined fronts. A prime condition governing development is the natural direction of the seam's perpendicular cleavage-planes, giving long lines of smooth faces near together and parallel, bearing about 65° to the left of the meridian and therefore crossing the basins. The gradients of dip into the basins change from 10 per cent at the east rim to practical flatness northwestward across the great coal-fields, a hundred miles wide; the clip being halved in rate at each successive crossing-over of an anticlinal crest. Elevations above sea-level on this transverse section, in scope of present development, differ by 1,000 ft. between low trough and high outcrop. Local irregularities of dip are found, but the main feature to be recognized is the pitch of the basins-the general rise northeastward at 20 ft. per mile, from 100 ft, below sea-level at the low point near the. SW. corner of Pennsylvania to 1,500 ft. and more above tide, and the appearance then, at the surface, of the lower coal-seams carried in the next deeper-lying thousand feet of rock-measures; below which series come the oil- and gas-sands of Oliphant's charted column of strata, reaching down altogether 3,000 ft. below the Pittsburg coal-seam. Because of -the general regularity of occurrence of the coal-seam, the mine-map depicting the courses of economic operation to be undertaken and the steps in controlled exhaustion, need be but a projection of two dimensions on the horizontal plane of space, and this for the most part composed of natural, almost unbroken lines, on the face and on the end of the coal, co-ordinating rectangularly.

Jul 1, 1910

By Lester Guttman

THE connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermo-dynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that called by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulae for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß-brass; 2. a- brass; 3. AuCu3; 4. AuCu. When the temperature is so high that no long-range order exists, these formulae reduce to the same form for all lattice types, namely: [ ] Here the symbols have the following meanings: [F-Helmholtz free energy E-energy S-entropy k-the gas constant per molecule z-coordination number, (e.g. 12 in. a-brass). N-total number of atoms c-atomic fraction of A] VAA, VBB, VAB-energy per bond of the corresponding bonds log means log, throughout The superscript 0 denotes the thermo- dynamic function in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition [ ] The free energy may also be written in terms of µA and µB, the chemical potentials or partial free energies per atom:

Jan 1, 1948

By P. W. Bakarian

PREVIOUS determinations1,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc-also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {102}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. EXPERIMENTAL METHOD Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 32 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. 2. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler's saw, rounded with a file and polishing paper to a diameter of 0.060 in, and evenly etched in dilute hydrochloric acid to a diameter of 0.038 ± 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1941

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult's law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa's4 data, and Kubaschewski7 has similarly treated Kawakami's7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By Sheldon P. Wimpfen

RESEARCH is undertaken to find out what must be done when what we are doing now is no longer adequate. To accomplish this end, researchers apply the truths of nature to industrial evolution. A survey conducted with the co-operation of 58 universities and colleges offering degrees in mineral engineering was the basis for the table accompanying this article. This survey was undertaken with the object of presenting to faculties and student bodies, as well as to industry, all available information on what action the educational institutions of the country have taken to provide the properly trained researchers so vitally needed. A hoped for result is that the great variety of opportunities available will encourage some undergraduate students to continue in their field beyond attainment of a B.S. degree.

Jan 1, 1947

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By R. M. Brown, W. J. Murphy, B. M. Kapadia

An investigatiott was conducted to study the influence of nitrogen, titanium, and zirconium on the boron llardenabilzty effect in a low-carbon constructiona2 alloy steel. The experimental steels investigated exhibited a significant variation in hardenability, the variation being dependent on the interactions of boron, titanium, and zirconium with the nitrogen. Only the boron not combined with nitrogen was effective in increasing hardenability. Titanium, and with lesser effectiveness zirconium, combined with available nitrogen, thereby protecting the boron. The hardenabil-ity effect mas related to an empirical expression for the "effective" boron content, P, deduced from experimental evidence of these interactions. The hardenabzlity effect reached a maximum at about 0.001 wt pct 0, and decreased somewhat as P increased further. The physical understanding of this relationship is discussed. FOR many years boron has been added to steels to obtain high hardenability. Although a great deal of research has been conducted on boron-treated steels, certain aspects of the boron hardenability effect have not been fully understood. For instance, the magnitude of the hardenability effect has been observed to vary markedly, depending on the steelmaking technique, even when the amount of boron in the steel was essentially constant. Furthermore, the optimum amount of this element to be added has not been definitely established. A better understanding of the boron hardenability effect is essential because too small an addition of boron is likely to be ineffective, while an excessive amount can cause brittleness'' and hot shortness. The findings of earlier investigations have shown that the hardenability effect cannot be consistently related to the amount of boron added or retained in the steel. Grossmann observed that in a 0.60 pct C steel the hardenability increased to a maximum with mold additions up to about 0.0025 pct B and then decreased with larger additions. Other investigators5 likewise reported a maximum in the hardenability at about 0.003 pct B. Crafts and Lamont, however, found that in commercial open-hearth heats of medium-carbon steel the hardenability increased linearly with boron up to 0.001 pct and remained essentially unchanged with larger percentages up to 0.006 pct. Other investigators7,' also observed a rather constant hardenability effect in the range about 0.0005 to 0.0035 pct B. These observations and other evidence suggest that the effectiveness of boron in increasing hardenability probably depends, in addition to the amount, on the form of boron retained in the steel, this form being influenced by the presence of other elements. Both oxygen and nitrogen apparently exert the strongest influence on the hardenability behavior, since, at the temperature of liquid steel, boron readily combines with these elements, thereby losing its effectiveness as most experimental evidence seems to indicate. For consistent recovery of the boron effective in increasing hardenability, it is necessary that the oxygen and nitrogen in the steel be either reduced to extremely small amounts by the steelmaking practice or neutralized by combination with other elements before the addition of boron. The importance of achieving adequate deoxidation prior to the addition of boron in order to realize the full hardenability effect of boron has been sufficiently emphasized by earlier investigators. Digges and Reinhart' and others have investigated the role of nitrogen and have shown that nitrogen also interacts with boron and reduces or nullifies altogether its effect on hardenability. Moreover, their work also demonstrated that the addition of strong nitride formers such as titanium and zirconium reduce the deleterious effect of nitrogen on boron hardenability by combining with nitrogen to form stable nitrides. Another element which has a pronounced influence on the boron hardenability effect is carbon. It has been shown7'10 that the hardenability effect of boron diminishes with increasing carbon content, and becomes almost negligible at the eutectoid composition. This observation is useful in comparing the potential increase in hardenability from boron of steels with different carbon contents, but is not relevant to a study of the effects of normal steelmaking variables. The amounts of oxygen and nitrogen in steel vary with the steel composition and steelmaking practice employed. Most commercia1 low-alloy steels are fully deoxidized by the addition of silicon and aluminum, or other strong deoxidizers, which adequately protect the boron from oxidation. In addition, one or more of the elements such as titanium or zirconium are usually added, either separately or in combination with boron, in the form of complex ferroalloys, to protect boron from combination with nitrogen in the steel. However, the actual amount and type of addition employed for a given processing requirement are usually selected by trial and error, and have a rather limited range of applicability. As a result, substantial variations in the hardenability of boron-treated steels are often observed in practice, particularly when the nitrogen content of the steel is a significant processing variable. These variations might therefore be reasonably attributed to the interactions between boron, nitrogen, and titanium or zirconium present in the

Jan 1, 1969

By Wilford L. Stork

Certain influences of oxygen on iron have been known for many years and it has always been considered one of the worst enemies of the iron and steel founders. Nobody had a good word for it, hence little was done to make use of this oxygen. In all the fields of foundry practice, the desideratum was "melt without oxidation of the metal." In the consideration of the influence of oxygen on cast iron, we must not confuse this condition with oxidized iron caused by poor melting conditions, due to a high bed, heavy charges, low coke ratio, excessive melting rate, high blast, or poor charging. It is admitted that oxygen absorbed by iron melted under these conditions has a deleterious effect on the properties of the iron. The writer has had experience both in the melting under such poor conditions and in remedying these bad conditions and considers the product far inferior to iron melted under normal conditions. As stated by Dr. Richard Moldenke,l such iron has a higher melting point and high combined carbon, is sluggish, and contains slags and oxides in solution in the liquid, causing slag inclusions and gas occlusions, 'thus producing defective castings. This oxidized condition cannot be counteracted or removed by any of the known deoxidizers; it can be remedied only by proper melting conditions. Such iron is redly burned, whereas the iron considered in this paper was melted under normal conditions with moderate blast, correct bed height, light charges of iron, and low coke consumption and is not in this category at all. In 1914, the late J. E. Johnson, Jr., startled the metallurgists of the . world when he published his results on the advantages of oxygen on cast iron.2 His work is so convincing and so logical, in spite of the common and well-established notions on the subject, that nobody has been able to refute a single argument. Such an eminent authority on iron and steel metallurgy as Prof. H. M. Howe has accepted the work in all its details in his latest book.3 The work of J. E. Johnson, Jr., has revolutionized the metallurgy of cast iron and it seems apparent that all future work must include an oxygen determination just as we include silicon, sul-

Jan 1, 1920

By A. A. Burr, D. Caplan

IN carrying out experiments in metal-gas systems, it is often difficult to estimate how long a reaction period must be allowed for equilibration. This is especially true in systems for which the diffusion coefficient is not known. In an investigation of the Cr-O system, the necessary information was obtained in the way described subsequently. Two pieces of chromium sheet of different thicknesses were packed in mixed powders of chromium and Cr2O3 and sealed into an evacuated metal capsule by welding. Austenitic stainless steel proved suitable as a capsule material up to 1350°C and molybdenum at higher temperatures. The capsule then was heated at a specific temperature for a time sufficient to saturate with oxygen the thinner but not the thicker specimen. The time is readily estimated from a preliminary experiment if a sufficient thickness differential is chosen. Under these experimental conditions, the metal sheet is exposed to a partial pressure of oxygen equal to that of the dissociation pressure of the oxide and hence can become saturated with oxygen without developing any second phase. After cooling, both samples were analyzed for oxygen by the vacuum fusion technique. Assuming that the surface of the specimens is kept saturated with oxygen throughout the experiment, the diffusivity can be calculated by application of the appropriate solution to Fick's second law. This is most conveniently accomplished by use of a plot of mean fractional saturation (Cm-Co) / (Cs-Co) vs (Dt) ½/L as given by Darken,' where t is time, L the half-thickness of the sheet, and D the diffusion coefficient. Cm, the mean concentration at time t, is given by the oxygen percentage in the thicker specimen; Cs, the constant surface concentration, is the oxygen percentage in the thinner specimen; Co is the oxygen content of the original chromium sheet. (Cm-Co) / (Cs-Co) is calculated and the corresponding (Dt) ½/L is read from the graph and D thereby calculated. By performing the experiment at two temperatures and plotting log D vs 1/T, the D for any temperature is established. (The activation energy for diffusion may be obtained from the slope of the line.) Once D is known as a function of temperature, it is a simple matter to estimate the correct reaction time for experiments with single specimens at other temperatures by equating (Dt) ½/L to its value for effective saturation. Darken' points out that this is approximately unity. The solubility of oxygen in chromium, as determined from the thin samples at each temperature, proved to be approximately 0.03 pct at 1350°C and less at lower temperatures. Due to low solubility and to the known difficulties of the vacuum fusion method in this low range, the values obtained for D (5x10-0 sq cm per sec at 1350°C) are estimated to be correct only within an order of magnitude. Nevertheless, the method has proved useful in estimating reaction times. Its usefulness will be greater in metal-gas systems where the solubility is appreciable. A second function of the method is to permit the determination of diffusion coefficients in systems for which the conventional techniques are experimentally difficult or impossible.

Jan 1, 1956

By FORTUNATO PEREIRA

(San Francisco Meeting, October, 1911.) I. GENERAL DESCRIPTION. The Department of Narino (formerly included in the Department of Cauca) is a narrow band about 170 km. (100 miles) wide in the southern part of the Republic of Colombia, FIG. 1.-SKETCH-MAP OF THE SOUTHWESTERN PART OF COLOMBIA. near the boundary of Ecuador, as shown in the sketch-map, Fig. 1. Its capital is Pasto, a small city of 25,000 inhabitants; the principal towns are Túquerres, Cumbal, Ypiales, Barbacoas, and Tumaco. The port on the Pacific ocean is Tumaco, and traffic in the interior is carried partly on the Patia river (steam navigation to the fluvial port of Barbacoas), and afterwards overland over poor roads by human bearers or on mule-back.

Aug 1, 1912

By AIME AIME

AMONG the European nations Germany is the center of interest economically as well as politically, and of prime importance for Europe as a whole is Germany's capacity to produce mineral products for armament and for export in exchange for the import of the essential supplies to maintain its industries. So far as minerals are concerned, Germany is worse off than any other great power except Italy, and deficiencies are being met by attempts to increase output from local deposits and by greater use of substitutes derived from domestic raw materials to replace imported metals, petroleum products, and other minerals.

Jan 1, 1939

KARL A. PAULY,* Schenectady, N. Y.-We are deeply indebted to Mr. Hobart for a record of the actual experience of the Lehigh Coal and Navigation Co. with electrification. One of the essential features of this test is that it was made under actual operating conditions. In one of the western mining districts I was once discussing the electrification of a large hoist with a mining operator, who told me that they had made a very thorough test and that the results were such as to indicate that electrification was not warranted. When questioned regarding the test, he said that they had called on the mining college in the Territory for assistance, and one of the instructors and a group of students had made the test. They first cleaned the boilers and then operated them at a' continuous load, using the maker's guaranteed steam consumption per indicated horsepower as a guide in estimating the steam consumption under actual hoisting conditions. Such a test is absolutely valueless. The efficiency of the boilers 'is affected by the intermittent demands on the steam. The standby losses, as indicated by Mr. Hobart's paper, are quite equal to the actual fuel consumption required to do the work; very frequently, also, the cost of repairs is either omitted or underestimated. One noticeable feature of Mr. Hobart's tabulation is that there is no mention of steam consumption. Intentionally or otherwise, the steam-hoist builders have befogged the question by making a great point of the steam consumption of hoists. The operator is not at all concerned in steam consumption; it is the actual cost of operation that he is interested in, and it is a comparison between the cost of operation of the two systems, all factors being considered, that should determine the choice. The steam consumption, or its determination by test, is only one step in the problem of estimating the fuel consumption, which, in an actual installation, can be directly measured much more accurately, as was done by Mr. Hobart.

Jan 4, 1918