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By A. M. Gaudin, R. T. Hukki

Previous work on the principles of comminution has shown: (I) that the surface produced is proportional to work input (Rittinger law,1a-3); (2) that there is regularity to the weight distribution of the fragments according to size.4-10 In this paper it is brought out that the surface on the fragments is distributed in definite and simple relation to size. The experimental work has involved: I. Construction of an apparatus capable of measuring the surface of mineral fragments independently of the chemical composition of the fragments and independently of the site of the surface; 2. Refining the methods available for measurement of particle size; 3. Designing and building a crusher capable of operating on very small quantities of mineral, if necessary on single crystals, and in such fashion as to minimize handling losses of material. Complete experiments have been carried out with massive quartz and individual quartz crystals. partial experiments, lacking surface measurements, have been made with glass spheres, galena, sphalerite, fluo-rite, salt and coal. Introduction The existence of regularity in weight distribution with size was noted many years ago, especially by A. 0. Gates;' the subject was also studied in detail by one of us.6 In the latter paper it was shown that rocks can be divided into two classes: homogeneous rocks, which show no preferential breaking, and heterogeneous rocks, which show preferential breaking at the grain size of the rock. It was shown, furthermore, that the fragments obtained by rupturing a homogeneous rock occur (in the fine range) in such abundance as to permit the writing of a relatively simple equation to relate the weight retained on a screen to the screen opening. With screens of which the openings are in constant ratio, the weight retained, w, is related to the screen size x by the equation w = Cxm [I] In this equation C and m are experimental constants. A plot of weight retained against particle size is a straight line of slope m if the scales for x and w are both logarithmic. In the fine range, the slopes of the size-distribution graphs plotted according to the method described above vary within a limited range. An inspection of a number of size-distribution data by various experimenters indicates that the slope very seldom exceeds 1.0, but is usually greater than 0.7. More recently, schuhmann8 proposed a method of charting that has so many advantages of its own that it has been used primarily in this work. For fine particles Schuhmann has found that the data are represented by the equation (x)m k [2]

Jan 1, 1947

By D. McLean

For many pu@oses uniform strength is desired over a long temperature range, coupled to a band of softness at the hot end for easy shaping. Various types of material fulfill such a requirement to different degrees, depending on the regularity of their atomic structure. In long-chain polymers and vitreous glasses the irregular structure leads to a steep temperature dependence of deformation resistance and the temperature band between the hard and brittle condition and the soft condition is only about 100 C. In crystals and especially metals the atomically regular structure leads to a much smaller sensitivity over a wide temperature band, thus approaching the ideal behavim. The reason for this insensitivity is that the regular crystalline structure deforms by the movement of dislocations and the elastic interactions of dislocations in- PLASTICS, GLASSES, AND CRYSTALS The ease or otherwise of deformation varies with temperature much more in some substances than in others. This is an important matter when service over a wide temperature range is needed, especially volve energies of several hundred electron volts compared with which the energy of thermal agitation is insignificant. However, temperature affects a metal's defmmation resistance through its influence on the annealing, m coarsening, of the three-dimensional dislocation network. This coarsening is a phenomenon very similar to grain growth and ideas about grain growth can be applied to it. Taking into account also the temperature dependence of the glide resistance from alloying additions, a reasonable account can be given of the overall effect of temperature on deformation strength and of stress and grain size on deformation rake. Special structures me described. some arising from these ideas and as yet untried, which may benefit metals and polymers but not ni-treous glasses. when in addition a degree of softness suitable for shaping is required at some stage. It would be nice if one could write on this subject in as much detail about plastics, glasses, and so forth, as about metals, but there has been far more study of this matter in metals than in other substances, which is one reason why most of this paper concerns metals. However, in Fig. 1 there are shown the deformation strengths of several nonmetallic substances as a function of temperature. In many tests the attempt at deformation caused breakage and the graph lines are then drawn dashed. Long-chain plastics, a glass, and a crystalline substance are included in Fig. 1. The notable feature of all of them is the sensitivity of the

Jan 1, 1969

Discussion of the paper of G. Howell Clevenger and Bhupendranath Ray, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2437 to 2475. ALLERTON S. CUSHMAN,* Washington, D. C.:-I am very much interested in the subject matter of this paper. I have had occasion to speak to this question before. There has recently been so much written and said and claimed about the effect produced by the addition of small quantities of copper to steel that there is certainly an impression abroad that a new and wonderful cure-all has been discovered. Are we facing a method of alchemy by which, at the expenditure of very little trouble and only a few cents' worth of copper per ton, the well-known characteristics of steel with respect to some features are so marvelously changed as in effect to produce a new metal ? I am a great believer in the future of the iron and steel alloy field. I do not think that with all the advances we have made in metallurgy we have begun to scratch the possibilities of usefulness to mankind in the exploration of the alloy field, and I include in that alloy field even what might be designated as the dilute alloy field; that is to say, where a very small quantity of a metal alloyed with iron and steel confers upon it some new or extraordinary qualities. With respect to many of the physical characteristics of the copper-iron or copper-steel alloys I am not particularly competent to speak. With respect, however, to the investigation of corrosion problems and with respect to claims made with regard to resistance to corrosion, I am competent to speak insofar as I have specialized to some extent in that field and have given up a great deal of my time for a great many years to a study of it. Some years ago, being particularly interested in the study of corrosion problems, I received the very generous permission of a large manufacturing concern to use their large open-hearth furnaces any way I saw fit for exploring this particular field. There is not a metallurgist in this room who will not realize the generosity of a manufacturing company who would permit a man to pursue a theory and give him as his material to work with 60 tons of molten metal. At all events, I threw copper into the open-hearth furnace. I explored this alloy field, not in a ittle crucible in which I had to take out portions and have them

Jan 12, 1913

By E. J. Rapperport, J. P. Pemsler

We have made calculations to evaluate the sensitivity of atomic absorption as a technique to measure vapor pressure changes with temperature. Our conclusion, supported by the experimental findings presented in this work, is that the ultimate sensitivity of the technique is well below lo-' Torr. This magnitude of vapor pressure sensitivity makes the method extremely attractive for thermodynamic studies. Atomic absorption techniques have been used previously in this connection by Scatchard and Boyd' and by vidale2 with a much lower sensitivity reported. Scatchard and Boyd's work measured cadmium pressure over Ag-Cd alloys in the range 0.02 to 0.3 Torr, and Vidale estimated that sensitivities of only 10"5 to 10"6 Torr are to be expected. Atomic absorption appears to be particularly well-suited to thermodynamic studies for several reasons: A) It is extremely sensitive; our experiments indicate an ability to measure vapor pressure changes of 10"9 Torr. B) It is highly selective; there is seldom interference among the resonant wavelengths of the various species. C) It may be performed in an absorption cell under static conditions. This alleviates such problems as surface impoverishment of alloys, attainment of equilibrium, and temperature measurement and control. D) Simultaneous, or near-simultaneous, vapor pressure measurements may be made for several elements in a given system. Experimental. The physical basis of the technique is the highly selective absorption of particular wavelengths by specific atomic species. In most atomic absorption work the element of interest is incorporated into a hollow cathode lamp to provide a characteristic spectral source of high intensity. The spectra lines characteristic of the element in the cathode are attenuated by atoms of that element in the radiation path. Radiation from silver or cadmium hollow cathode lamps was directed along a path containing a 10-cm evacuated silica cell. The cell was positioned within a silica windowed furnace and contained silver, cadmium, or an Ag-Cd alloy. As the furnace temperature was elevated, the number of atoms of the absorbing element in the vapor phase within the cell rose, and the resonant radiation was increasingly absorbed. Intensities were measured by passing the radiation through a Techtron Model AA-4 one-half meter grating atomic absorption spectrometer equipped with a photo-multiplier detector. In order to minimize instabilities in the source, the hollow cathodes were allowed to warm up for several hours and were run at only 2 5 to 30 pct of their maximum rated amperage. In addition the attenuated beam was monitored before and after each reading. The attenuation of resonant wavelengths may be related to vapor pressure by the following relationships.

Jan 1, 1969

By R. W. Woodward, G. K. Burgess

minum bronze. Nearly all copper-base alloys are improved by rolling processes, but the copper-aluminum alloys seem to possess equally good properties when cast or rolled; this is a remarkable metallurgical fact. Another important property of these copper-aluminum alloys is their resistance to alternating stress. Many tests indicate that their resistance is greater in this respect than that of some steels, and I have seen instances when cast aluminum-bronze bolts have outlived five steel bolts in foundation work subject to severe shocks. I mention these various instances to indicate that work originally started as research for substitution of one material for another frequently develops 212 article which has properties not possessed by the original metal or alloy. I have dwelt particularly on the aluminum bronzes because recently I have done more special work on them than on other alloys, but I believe that the use of aluminum itself, in many combinations of metals, is a very important subject for investigation. Undoubtedly, after the war, the cost of aluminum will be reduced from its present price, and considering its low specific gravity it offers a very interesting and important field for research in the non-ferrous business. Naturally, if combinations containing aluminum can be developed in view of a probably increasing supply of metal, the cost will be reduced. This will benefit the industry generally and will immediately conserve tin. Bronzes, Bearing Metals, and Solders G. K. Burgess* and R. W. Woodward,† Washington, D. C.— From a metallurgical standpoint, there are several ways in which a reduction of the tin consumed in commercial non-ferrous and white-metal alloys can be effected. First, a reduction of the tin content of the alloy; second, substitution of part or all of the tin content by some other metal; third, a substitution of a different type of alloy, which in some cases also involves a change in mechanical design. The Bureau of Standards has been studying these methods of conservation for tin alloys, particularly in regard to babbitts and bearing metals, bronzes, and solders. Much of the information sewed by the Bureau was obtained from answers to questionnaires sent to manufacturers and users of these materials, so that, in general, any of the following suggestions or recommendations can be considered as being practical and as having already been thoroughly tried. Bearing Metals There is no question that the tin content of nearly all bearing metals can be reduced to some extent, and in some cases actually eliminated

Jan 1, 1919

In reply to inquiries and comments which have reached me since the publication of this paper, and in explanation of some seeming discrepancies between my statements in the text concerning the amount of displacement of the faults, on one hand, and certain figures in the plates on the other hand, I give here, with some additional remarks, my measurements of the displacements in the different sections, which it originally seemed unnecessary to print : By displacement, I mean neither the throw, i.e., the vertical distance apart of the two edges of a faulted bed (what Mr.

Jan 1, 1896

By M. Gell, G. R. Leveran

The high- and low-cycle fatigue properties of the nickel-base superalloy, Mar-MBOO, in columnar-grained and single-crystal forms were determined at room temperature. It was found that the fatigue lives of these materials were greatly affected by the size of preexisting cracks in MC-type carbides contained in the micro structure. Most of the data falls on two curves given by: (zN)'/A€= K, where Nf is the number of cycles to failure, Af is the total strain range, and K is a function of carbide size. No difference was observed in the fatigue behavior of the columnar-grained and single-crystal materials for the same MC carbide size. Matrix slip and crack initiation occurred at precracked MC carbides and, to a lesser extent, at micropores. Fatigue crack propagation was mainly in the Stage I mode, i.e., on cry stallo graPhic slip planes. The Stage I fracture in these materials was unusual in that distinct features were observed on the fracture surfaces. In high-cycle fatigue, these features resembled those commonly observed on the cleavage fracture surfaces of bcc and hcp materials. Yet, in this study, the cracks propagated slowly in a cyclic manner. In low-cycle fatigue, the Stage I facets contained equiaxed dimples, similar to those observed on the tensile fracture surfaces of ductile materials. These observations indicate that both local normal and shear stresses are involved in these Stage I fractures. A model is proposed to explain these results based on the weakening of the cohesive energy of the active slip planes by reversed shear deformation and the fracture of the bonds across the weakened planes by the local normal stress. RECENT developments in casting technology have produced cast nickel-base superalloys in columnar -grained and single-crystal forms.1'2 The tensile and creep properties of the nickel-base superalloy, Mar-M200, cast in these forms have been shown to be superior to the corresponding properties of the conventionally cast polycrystalline material.lp2 This improvement in properties results, in part, from the elimination of grain boundaries in the single crystals and the alignment of the grain boundaries parallel to the stress axis in the columnar-grained castings. As part of a program to evaluate the fatigue properties of nickel-base superalloys cast in single-crystal and columnar-grained forms, a study has been made of the cyclic deformation and fracture of Mar-M2OO at room temperature. M. fiFl I .hininr Mpmher AIMF ic ^pninr Rocoarrh Accn^iata anH I) EXPERIMENTAL PROCEDURE The composition range of Mar-Ma00 in weight percent is: 8 to 10 Cr, 9 to 11 Co, 11.5 to 13.5 W, 0.75 to 1.25 Cb, 1.75 to 2.25 Ti, 4.75 to 5.25 Al, 0.01 to 0.02 B, 0.03 to 0.08 Zr, 0.07 to 0.12 C, bal. Ni. All of the castings met the above specifications. The castings were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr which resulted in a 0.2 pct offset yield stress of 150,000 psi at room temperature. The microstructure of the material consisted of cuboidal, coherent particles of ordered, fcc Ni3(A1,Ti) (commonly designated y'), approximately 0.3 p on edge, distributed in an fcc y solid-solution matrix. MC carbides together with shrinkage and gas micropores were also distributed throughout the materials. The MC carbides and micropores were located preferentially in the interdendritic interstices, as well as in the grain boundaries in the columnar-grained castings. The (100) direction of all the single crystals and the common (100) axis of the grains in the columnar materials were aligned within about 5 deg of the specimen axis. Fatigue testing was carried out in the high-cycle (HCF) and low-cycle (LCF) fatigue regions, with the major difference being gross yielding of the specimen occurred during the first cycle in the LCF region. This division also corresponded with the more usual one in which the life of a specimen in LCF is less than lo4 cycles and that in HCF is greater than lo4 cycles. The designs of the high-cycle fatigue and low-cycle fatigue specimens are shown in Figs. l(a) and (c), respectively. The gage sections of both HCF and LCF specimens were electropolished prior to testing. The HCF specimens were tested in an MTS, closed-loop, hydraulic fatigue machine at 10 cps in air. The specimens were cycled between a tensile stress of 5000 psi and a maximum tensile stress which ranged from 35,000 to 125,000 psi, Fig. l(b). The LCF specimens were cycled under strain control from zero to a maximum tensile strain, Fig. l(d), in a Wiedemann-Baldwin testing machine. The experimental procedure has been described elsewhere.3'4 Both HCF and LCF tests were interrupted periodically in order to replicate the development of slip and cracking at the specimen surface. This was accomplished by placing plastic replicating tape around the gage section of the specimen while the specimen was in the mahine. The size of the MC carbides for all specimens was measured on a polished longitudinal section through the gage section after fatigue testing. The method of measurement consisted of carefully scanning the entire polished section in order to locate the largest MC carbides. Photographs were then taken of the six longest carbides oriented approximately normal to the

Jan 1, 1969

By I. J. Demer, M. L. Holzworth, J. C. Kremer, P. A. Beck

For alloys which are in practice heat treated to obtain increased strength, such as steels, duralumin, copper-beryllium, and others, the treatment usually involves heating to a relatively high temperature. At such temperatures the grain size of the product is largely determined by grain growth. Even in metals and alloys annealed merely to relieve work hardening, recrystal-lization is generally followed by a certain amount of grain growth. Thus, effective grain size control, which is often of great practical importance in manufacturing processes, depends on the grain growth behavior of the material used. Despite its importance, grain growth has been the subject of few investigations of a fundamental nature. The term "grain growth" has been used to designate a group of related, but distinctly different, phenomena. The two most important and best known of this group are illustrated by the following example. Curve a in Fig I shows the increase of the average grain size of a copper-beryllium alloy, containing 2 pct Be and 0.15 pct Co, with increasing annealing temperature. The time of annealing was 2 hr. The grain size was quite uniform in all specimens. The results of a similar experiment with an alloy containing 2 pct Be and 0.31 pct Co are shown by curve b It is seen that for any annealing temperature below T, the grain size was smaller than. in the previous case. Grain growth became slower with the higher Co content. This "inhibiting" effect of the higher Co addition was associated with the appearance in the microstructure of fine, light blue particles of the CoBe phase. Up to temperature T, the structure of the inhibited alloy (curve b) was just as uniform as the structures represented by curve a. However, after annealing at T or at higher temperatures, the inhibited alloy showed some extremely large grains (much larger than the grain sizes developed by the uninhibited alloy with low Co content) mixed with the small grains according to curve b. The presence of these mixed or "duplex" structures is indicated in Fig I by the vertical lines branching off curve b. The type of grain growth occurring in uninhibited Cu-Be alloys (curve a) has been most frequently and best investigated in brass. This type has been designated as "normal grain growth,'' while the grain growth phenomena occurring in inhibited materials were, at times, referred to as "abnormal grain growth." However, since the latter term has been applied occasionally to the phenomenon of critical recrystallization, which also results in large grains although by an entirely different mechanism, in the present paper a different nomenclature has been adopted in order to avoid confusion. Typical of the grain growth in uninhibited metals and alloys is the continuous

Jan 1, 1949

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By Rufus J. Foster

During the discussion on the Preparation and Utilization of Sniall Sizes of Anthracite (page 613 of present volume), several inquiries were made concerning the use of the McClave grate, which was mentioned by Mr. Coxe as having proved satisfactory in the generation of steam at his collieries, and also at a large number of industrial estal)lishments in Scranton and elsewhere. For a more satisfactory repIy to such inquiries than could be furnished in the oral discussion, I have prepared the following paper to be included in the published proceedings. And, as the use of the fuel under consideration necessarily requires the employment of a blower to change the fire, from a condition giving an incandescent radiant heat only to one giving a hot gaseoua flame as well, I shall add a description of the McClave Argand blower and its method of action. The grate and blower combined form a complete and effective system fcr burning small fuels, such as anthracite culm, birdseye, buckwheat, bituminous slack, etc., in boiler and other furnaces; while the grate alone is now extensively used with the larger sizes of hard and soft coal in furnaces where blast is riot required. Fig. 1 is a view of the RlcClave grate as built in two sections. It is constructed on the principle best approved by practice to prevent warping and burning out; that is, it presents no long lines of

Jan 1, 1892

The Joint Session on Continuous Cast- ing, of the Institute of Metals Division and the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers, convened in the Jade Room of, the Hotel Waldorf-Astoria, New York City, on Feb. 23, 1944, at 9:15 o'clock, Carl E. Swartz presiding. C. E. SWARTZ.-It is gratifying to see so many out at what may seem an early hour for the beginning of A.I.M.E. sessions, but I think this number-some fifty or sixty of you-is an adequate expression of the interest in these processes all over the United States, and possibly in foreign countries. I would like to ask those who feel that this type of program is of value to you to write or speak to some one of the Institute of Metals Division officers and suggest other topics for symposiums. We have a feeling that some of these current practices are of interest and we believe that under proper sponsorship many of the companies will be willing to give publicity to processes such as those that will be discussed today. Also, we would like suggestions and criticisms, so that the next ones can be better. The subject of continuous casting is not new, of course. The two papers on the program this morning will adequately cover the history and some of the earlier processes, some of the theory and some of the practice, some of the reasons why these various methods did not work. I was rather interested in discovering, when thumbing through one of the A.I.M.E. publications the other night, an article on continuous casting. I was not aware that the A.I.M.E. had published any papers on continuous casting, but there may be a number. The one that I happened to find was published in the 1915 volume, on the Mellen rod- casting process, and so we might say this is not the first session in which these subjects have been under discussion. However, there have been many improvements since then in all fields of metallurgical and mechanical engineering; consequently, I think that the papers today will be a little more involved and a little more complete in their technique. The first paper today will be given by one of our gentlemen of the press, who has done one of the outstanding jobs in this country in calling to our attention some of the newer processes that are being considered and being used in the metallurgical indus-

Jan 1, 1945

By J. J. Lander, L. H. Germer

MOLYBDENUM and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved only limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150'C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1947

By J. J. Lander, L. H. Germer

Molybdenum and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved onlv limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150°C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1949

By R. W. Raymond

ChaRles William HenRy Kirchhoff was born March 28, 1853, at San Francisco, Cal., where his father, Charles Kirchhoff, was at that time consul for his native country, Germany. A few years later, the family moved' to Hoboken, K. J., in which city the son received his preliminary education at the Hoboken Academy, proceeding later to Germany, where he was graduated in 1874 as mining engineer and metallurgist at the Prussian Royal Mining Academy of Clausthal, in the Harz. Upon his return to the United States, he became chemist of the Delaware Lead Refinery at Philadelphia, and retained that position for three years. But in 1877 he began what was to be an almost uninterrupted life-long association with David Williams, the publisher of The Iron Age, of New York, who established in that year, and continued for a brief period, a journal entitled the Metallurgical Review, on the editorial staff of which Mr. Kirchhoff received a place. The enterprise was doubtless an attempt to cover a wide metallurgical field outside of that which properly belonged to The Iron Age. But it was soon abandoned, and Mr. Williams wisely concentrated his energies upon the older journal, which, under his vigorous and skillful management, and the labors of the able editors and correspondents whom he selected, became one of the greatest institutions of its class in the world. From 1878 to 1881, Mr. Kirchhoff was assistant editor of The Iron Age. From 1881 to 1884, he was managing editor of the Engineering and Mining Journal; in 1884 he returned to The Iron Age, to become for five years its associate editor, and in 1889, on the retirement of James C. Bayles, editor-in-chief. This list of dates and employments, without further comment, sufficiently indicates, at least to the eye of an expert, that Mr. Kirchhoff had found his congenial career in trade journalism. His qualifications for this profession were somewhat exceptional. He possessed the scientific training, the knowledge of foreign languages and literatures, and the power of making and keeping friends, which enabled him to get early notice of technical novelties; he had the taste for statistics which made him both industrious and intelligent in their collection and use; and to these traits he added a mastery of the meaning of such accumulated data, and a sane, critical judgment of the situations which they represented, as well as of the sources and the figures themselves, which made his opinion weighty

Jan 1, 1917

By W. A. Bates, R. J. Miller

Although cresylic acids have been standard frothers in flotation for many years, there has been little discussion of their nature in the metallurgical literature. Aside from references in the patent literature, the paper by Landolt, Hill, and Lowyl in 1930, which resented a study of the frothing and collecting properties of some of the constituents of crude cresylic acids, represents the only contribution of this type. The close froth control required in the delicate selective separations of present-day flotation operations have required the flotation metallurgist to choose his frothers with care, and have caused him to require of the manufacturer a closely controlled, uniform product. A background of knowledge of the chemical composition and physical and chemical properties of the frothers, by which their action may be correlated, should aid in selecting frothers for particular flotation requirements. Further, the recent almost complete replacement in flotation of coal-tar cresylic acids by those derived from petroleum makes it especially desirable to review the flotation behavior of the acids from the old and the new sources. In view of these facts the Milling Methods Committee of the A.I.M.E. suggested to the Oronite Chemical Co. of San Francisco the preparation of a paper on the subject, and this paper has accordingly been prepared as a contribution by the California Research Corporation, the research affiliate of the Oronite Chemical Co. The discussion is from the following aspects: (I) constitution and properties; (2) sources; (3) comparison of coal-tar and petroleum cresylic acids; (4) characteristics as frothers, with particular reference to the effect of the substitution of petroleum acids for coal-tar acids. Constitution and Properties Cresylic acids are commonly regarded as mixtures of orthocresol, metacresol and paracresol. This was, indeed, the former meaning of the term, but in recent years it has been loosely applied to any mixture of alkyl phenols boiling above 190°C.; that is, excluding only phenol itself. This means that cresylic acids, as they are known today, may consist of mixtures, not only of the three isomeric cresols, but of six xylenols and of a variety of higher boiling homologues. Generically the constituents of cresylic acids are alkyl phenols, and they are often so designated in the literature to avoid the more indefinite term, "cresylic acids." They form an homologous series starting with phenol, which has the familiar benzene ring, with an hydroxyl group in place of one of the hydrogen atoms. The series of alkyl phenols is formed by the substitution of alkyl side chains, such as methyl, ethyl, propyl, butyl, etc., for hydrogen atoms of the benzene ring of phenol. Some

Jan 1, 1947

By R. J. Miller, W. A. Bates

Although cresylic acids have been standard frothers in flotation for many years, there has been little discussion of their nature in the metallurgical literature. Aside from references in the patent literature, the paper by Landolt, Hill, and Lowyl in 1930, which resented a study of the frothing and collecting properties of some of the constituents of crude cresylic acids, represents the only contribution of this type. The close froth control required in the delicate selective separations of present-day flotation operations have required the flotation metallurgist to choose his frothers with care, and have caused him to require of the manufacturer a closely controlled, uniform product. A background of knowledge of the chemical composition and physical and chemical properties of the frothers, by which their action may be correlated, should aid in selecting frothers for particular flotation requirements. Further, the recent almost complete replacement in flotation of coal-tar cresylic acids by those derived from petroleum makes it especially desirable to review the flotation behavior of the acids from the old and the new sources. In view of these facts the Milling Methods Committee of the A.I.M.E. suggested to the Oronite Chemical Co. of San Francisco the preparation of a paper on the subject, and this paper has accordingly been prepared as a contribution by the California Research Corporation, the research affiliate of the Oronite Chemical Co. The discussion is from the following aspects: (I) constitution and properties; (2) sources; (3) comparison of coal-tar and petroleum cresylic acids; (4) characteristics as frothers, with particular reference to the effect of the substitution of petroleum acids for coal-tar acids. Constitution and Properties Cresylic acids are commonly regarded as mixtures of orthocresol, metacresol and paracresol. This was, indeed, the former meaning of the term, but in recent years it has been loosely applied to any mixture of alkyl phenols boiling above 190°C.; that is, excluding only phenol itself. This means that cresylic acids, as they are known today, may consist of mixtures, not only of the three isomeric cresols, but of six xylenols and of a variety of higher boiling homologues. Generically the constituents of cresylic acids are alkyl phenols, and they are often so designated in the literature to avoid the more indefinite term, "cresylic acids." They form an homologous series starting with phenol, which has the familiar benzene ring, with an hydroxyl group in place of one of the hydrogen atoms. The series of alkyl phenols is formed by the substitution of alkyl side chains, such as methyl, ethyl, propyl, butyl, etc., for hydrogen atoms of the benzene ring of phenol. Some

Jan 1, 1947

By Carl E. Swartz

The Joint Session on Continuous Casting, of the Institute of Metals Division and the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers, convened in the Jade Room of the Hotel Waldorf-Astoria, New York City, on Feb. 23, 1944, at 9:15 o'clock, Carl E. Swartz presiding. C. E. SWartz.—It is gratifying to see so many out at what may seem an early hour for the beginning of A.I.M.E. sessions, but I think this number-—some fifty or sixty of you —is an adequate expression of the interest in these processes all over the United States, and possibly in foreign countries. I would like to ask those who feel that this type of program is of value to you to write or speak to some one of the Institute of Metals Division officers and suggest other topics for symposiums. We have a feeling that some of these current practices are of interest and we believe that under proper sponsorship many of the companies mill be willing to give publicity to processes such as those that will be discussed today. Also, we would like suggestions and criticisms, so that the next ones can be better. The subject of continuous casting is not new, of course. The two papers on the program this morning will adequately cover the history and some of the earlier processes, some of the theory and some of the practice, some of the reasons why these various methods did not work. I was rather interested in discovering, when thumbing through one of the A.I.M.E. publications tile other night, an article on continuous casting. I was not aware that the A.I.M.E. had published any papers on continuous casting, but there may be a number. The one that I happened to find was published in the 1915 volume, on the Mellen rod-casting process, and so we might say this is not the first session in which these subjects have been under discussion. However, there have been many improvements since then in all fields of metallurgical and mechanical engineering; consequently, I think that the papers today will be a little more involved and a little more complete in their technique. The first paper today will be given by one of our gentlemen of the press, who has done one of the outstanding jobs in this country in calling to our attention some of the newer processes that are being considered and being used in the metallurgical indus-

Jan 1, 1945

By R. J. Miller, W. A. Bates

ALTHOUGH cresylic acids have been standard frothers in flotation for many years, there has been little discussion of their nature in the metallurgical literature. Aside from references in the patent literature, the paper by Landolt, Hill, and Lowy1 in 1930, which presented a study of the frothing and collecting properties of some of the constituents of crude cresylic acids, represents the only contribution of this type. The close froth control required in the delicate selective separations of present-day flotation operations have required the flotation metallurgist to choose his frothers with care, and have caused him to require of the manufacturer a closely controlled, uniform product. A background of knowledge of the chemical composition and physical and chemical properties of the frothers, by which their action may be correlated, should aid in selecting frothers for particular flotation requirements. Further, the recent almost complete replacement in flotation of coal-tar cresylic acids by those derived from petroleum makes it especially desirable to review the flotation behavior of the acids from the old and the new sources. In view of these facts the Milling Methods Committee of the A.I.M.E. suggested to the Oronite Chemical Co. of San Francisco the preparation of a paper on the subject, and this paper has accordingly been prepared as a contribution by the California Research Corporation, the research affiliate of the Oronite Chemical Co. The discussion is from the following aspects: (I) constitution and properties; (2) sources; (3) comparison of coal-tar and petroleum cresylic acids ; (4) characteristics as frothers, with particular reference to the effect of the substitution of petroleum acids for coal-tar acids. CONSTITUTION AND PROPERTIES Cresylic acids are commonly regarded as mixtures of orthocresol, metacresol and paracresol. This was, indeed, the former meaning of the term, but in recent years it has been loosely applied to any mixture of alkyl phenols boiling above 190°C.; that is, excluding only phenol itself. This means that cresylic acids, as they are known today, may consist of mixtures, not only of the three isomeric cresols, but of six xylenols and of a variety of higher boiling homologues. Generically the constituents of cresylic acids are alkyl phenols, and they are often so designated in the literature to avoid the more indefinite term, "cresylic acids." They form an homologous series starting with phenol, which has the familiar benzene ring, with an hydroxyl group in place of one of the hydrogen atoms. The series of alkyl phenols is formed by the substitution of alkyl side chains, such as methyl, ethyl, propyl, butyl, etc., for hydrogen

Jan 1, 1946

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963