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By C. C. Henning

IN any line of human activity logical handling requires an amount of attention to each phase that is in keeping with the importance of that phase. In the complex and rapidly changing field of modern ferrous metallurgy it is difficult to allot the proper degree of attention to the various subjects, and it is not surprising that one or more subjects of major importance should for a time be neglected. Bessemer steel is a good example of a neglected subject. It is largely taken for granted, inferior physical quality is assumed for it, and there is a lack of interest in its technical development and commercial application. Availability of supply is limited. In spite of this technical indifference, limited source and lack of commercial exploitation, bessemer steel constitutes a large volume of tonnage in daily use. There is a fairly prevalent idea even among technical people that bessemer steel survives mostly because of low cost and by reason of a dwindling residue of applications sufficiently common to permit of its use. The difference in cost between bessemer and open-hearth steel is governed largely by the relative cost of manufacture of pig iron and the market price of steel scrap. During the past four years there have been long periods of time during which the price of steel scrap was low enough so that open-hearth steel was considerably lower in manufacturing cost than bessemer. As to application, it may be pointed out that thousands of tons of this material in the form of bessemer screw steel are applied for moving parts in automotive and other equipment, Some forging work and considerable heat treating, particularly carburizing, is performed on this grade. From an economic standpoint the most effective contribution of bessemer steel lies in its free machining qualities. It is by far the freest

Jan 1, 1935

By W. M. Peirce

Commencing in 1922, each year a lecture has been presented to the Institute of Metals Division at this February meeting. The range of subjects has been very- broad. Some speakers have dealt with the most advanced work in the very heart of the science of physical metallurgy. Others have stimulated our imaginations by discussing the most recent progress in related fields of science. Others have told us of the latest art, which is at any moment of greater practical importance than the latest science, of metals. I feel that this broad precedent in the choice of subjects will justify my choosing to talk about some of the prosaic details of how, during the last generation, industry has effectively organized research to accelerate progress in our own and all other fields of science and related art. A number of years ago I visited one of this country's well-known research laboratories and had the pleasure of chatting for a few minutes with its equally well-known director. Being particularly interested at the time in the organization problems connected with industrial research, I broached that subject. My host stated in effect that he didn't believe in organized research. He was, of course, resorting to a rhetorical hyperbole. to pain: out the danger of overorganization which can so easily drift into regimentation and destroy individual initiative. Actually nearly all of us, much as we cherish our personal freedom of action, believe in organization because the history of progress in every field of human activity has been a history of men learning to work together, to cooperate, to create an efficient division of labor. We use organization to achieve this coordination. At the same time our form of organization must not stifle individual initiative or it will prove a deterrent rather than an aid to accomplishment. Research, too, must be organized for greatest achievement but especial skill and care are perhaps needed to avoid stifling the initiative of the individual workers. I have, of course, followed with keen interest and much benefit the vast amount . that has been said and written on this subject in the past twenty years but I still find new stimulation in discussions with my good friends working in this field. It is my hope that this discussion may serve a like purpose. It would be ungracious not to make due acknowledgment to the many able contributors to this particular phase of human progress, but their very number and the great volume of their writing makes it impossible to trace to any one individual a particular significant and valuable idea. I shall content myself therefore with this general acknowledgment and with acknowledgment of the specific debt that every research man owes to those who have so ably kept before the public, and in particular before industrial executives, the place of research in the modern scheme of things' Because of the legitimate publicity thus given to research, the day is past when any

Jan 1, 1944

By W. M. Peirce

Commencing in 1922, each year a lecture has been presented to the Institute of Metals Division at this February meeting. The range of subjects has been very- broad. Some speakers have dealt with the most advanced work in the very heart of the science of physical metallurgy. Others have stimulated our imaginations by discussing the most recent progress in related fields of science. Others have told us of the latest art, which is at any moment of greater practical importance than the latest science, of metals. I feel that this broad precedent in the choice of subjects will justify my choosing to talk about some of the prosaic details of how, during the last generation, industry has effectively organized research to accelerate progress in our own and all other fields of science and related art. A number of years ago I visited one of this country's well-known research laboratories and had the pleasure of chatting for a few minutes with its equally well-known director. Being particularly interested at the time in the organization problems connected with industrial research, I broached that subject. My host stated in effect that he didn't believe in organized research. He was, of course, resorting to a rhetorical hyperbole. to pain: out the danger of overorganization which can so easily drift into regimentation and destroy individual initiative. Actually nearly all of us, much as we cherish our personal freedom of action, believe in organization because the history of progress in every field of human activity has been a history of men learning to work together, to cooperate, to create an efficient division of labor. We use organization to achieve this coordination. At the same time our form of organization must not stifle individual initiative or it will prove a deterrent rather than an aid to accomplishment. Research, too, must be organized for greatest achievement but especial skill and care are perhaps needed to avoid stifling the initiative of the individual workers. I have, of course, followed with keen interest and much benefit the vast amount . that has been said and written on this subject in the past twenty years but I still find new stimulation in discussions with my good friends working in this field. It is my hope that this discussion may serve a like purpose. It would be ungracious not to make due acknowledgment to the many able contributors to this particular phase of human progress, but their very number and the great volume of their writing makes it impossible to trace to any one individual a particular significant and valuable idea. I shall content myself therefore with this general acknowledgment and with acknowledgment of the specific debt that every research man owes to those who have so ably kept before the public, and in particular before industrial executives, the place of research in the modern scheme of things' Because of the legitimate publicity thus given to research, the day is past when any

Jan 1, 1944

By H. W. Hitzrot

The new 4800-ton fine-grinding plant at the Hollinger Consolidated Gold Mines property at Timmins, in the Porcupine district of northern Ontario, went into operation in November 1937, and represents the culmination of an experimental program. The plant is a moderately low rectangular building of hollow tile on a steel frame, large enough to house four 7 by 15-ft. ball mills, with a 12 by 27-ft. classifier beside each mill. At one end is space for the addition of another mill and classifier or a mill and classifier for the regrinding of table concentrates. This regrinding is now done in the old grinding department of the main mill building. Also within the new building are the four 6-in. sand pumps for lifting the product from the low-dis-charge ball mills up to the classifier feed launders and the containers and appurtenances of a complete dust-collecting system. Together with the usual overhead crane, these constitute the major units of equipment within the new plant. The location is at the lower end of the main mill buildings toward the old tailings pond, now so neatly leveled off and sodded to rival the very best of our own W.P.A. projects. Close by the new grinding plant is a large dome-shaped structure—the new fine-ore bin designed and built by Mr. Longmore and the Hollinger milling and engineering staffs. There are four separate automatically loaded inclined belt conveyors leading up from the bottom of the bin to the grinding plant. Each belt is equipped with a recording weightometer, in the grinding building. The whole structure and the machinery within it give the impression of permanence and a carefully integrated design with close attention to details, giving the operators every advantage for consistently good work. The many ideas and opinions behind this achievement were all ably organized and executed by the Hollinger milling and engineering staffs, and not a few were directly initiated by them. Excellent cooperation was afforded by the Hollinger staff to the engineers helping to conduct

Jan 1, 1939

By H. W. Hitzrot

The new 4800-ton fine-grinding plant at the Hollinger Consolidated Gold Mines property at Timmins, in the Porcupine district of northern Ontario, went into operation in November 1937, and represents the culmination of an experimental program. The plant is a moderately low rectangular building of hollow tile on a steel frame, large enough to house four 7 by 15-ft. ball mills, with a 12 by 27-ft. classifier beside each mill. At one end is space for the addition of another mill and classifier or a mill and classifier for the regrinding of table concentrates. This regrinding is now done in the old grinding department of the main mill building. Also within the new building are the four 6-in. sand pumps for lifting the product from the low-dis-charge ball mills up to the classifier feed launders and the containers and appurtenances of a complete dust-collecting system. Together with the usual overhead crane, these constitute the major units of equipment within the new plant. The location is at the lower end of the main mill buildings toward the old tailings pond, now so neatly leveled off and sodded to rival the very best of our own W.P.A. projects. Close by the new grinding plant is a large dome-shaped structure—the new fine-ore bin designed and built by Mr. Longmore and the Hollinger milling and engineering staffs. There are four separate automatically loaded inclined belt conveyors leading up from the bottom of the bin to the grinding plant. Each belt is equipped with a recording weightometer, in the grinding building. The whole structure and the machinery within it give the impression of permanence and a carefully integrated design with close attention to details, giving the operators every advantage for consistently good work. The many ideas and opinions behind this achievement were all ably organized and executed by the Hollinger milling and engineering staffs, and not a few were directly initiated by them. Excellent cooperation was afforded by the Hollinger staff to the engineers helping to conduct

Jan 1, 1939

By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

JESSE L. JONES,* Pittsburgh, Pa.-I would like to ask Miss Erskine if down-draft has been used in any of the foundries where heavy fumes have to be removed, instead of the overhead draft.? L. -ERSKINE.-The system of overhead draft to remove heavy fumes has been very much more successful. The entire efforts of the New Jersey Department of Labor in regard to stabilizing conditions in the foundry are the result of the physical examination of the foundryman himself on first-hand information as to the prevalence of the minor ailments and the bad timekeeping that naturally accompanies them. These ailments are a factor in not only increasing the labor turnover but in increasing the percentage of bad work as well. The physical exertion of the foundryman himself is of course an important factor. In certain standard shops the amount of energy expended runs from 11 to 13 tons of foot-pounds of energy a day. In certain shops on piece work, I found a record of the energy expended per day to run as high as 22 tons. In one shop, during the war period, the management established a bonus system, and the men increased their output from 60 to 100 molds a day. The result was an increase of some 60 per cent. in output, and an increase of 400 per cent. in defective castings. The question of the physical exertion in the unsanitary foundries, of course, is very much complicated by other factors, for which reason the department has devoted a good deal of attention to estimating what is a reasonable exertion in a sanitary, well ventilated foundry. We have met certain physical difficulties in the brass foundries that the iron foundries did not have. All that information is available through our Bureau of Industrial Information. The question of the physical energy exerted by the molder is found to have a very distinct bearing on the question of contracts, for the possibility of increasing production is balanced by the extra overhead involved. JESSE L. JONES.-I would like to ask if any evidence has been noticed of carbon-monoxid poisoning among the employees of the foundries.

Jan 4, 1919

By E. T. Turkdogan, J. H. Swisher

The solubility of oxygen in zone-refined iron was determined in the temperature range.from 881" to 1350°C. The solubility in a iron at 881°C ms found to be about 2 to 3 ppm; in y iron, the solubility was found to increase from about 2 to 3 ppm at 950°C to about 25 ppm at 1350°C. The permeability of oxygen in an iron -0.1 pct Al alloy was determined in the y iron range, using an internal oxidation technique. By combining the permeability and solubility data, the diffzisivity of oxygen in y and a iron was calculated. The oxygen diffusivity in solid iron may be s~immarized as follows: 8820 For 6 iron and IN a recent paper, Hepworth, Smith, and Turkdogan1 reported on the solubility, permeability, and diffusivity of oxygen in 6 iron, together with permeability data for oxygen in a iron. In the present investigation, similar measurements were made in the ? phase region. In addition, a solubility measurement was performed in the a phase region to permit calculation of the diffusivity of oxygen in a, iron. References to early work on this subject are given in the previous publication.' EXPERIMENTAL Solubility Measurements. The oxygen solubility was determined by equilibrating cylindrical samples 0.3 in. diam by 14 in. long of zone-refined iron in water vapor-hydrogen gas mixtures. The zone-refined iron was prepared by B. F. Oliver of this laboratory, using an apparatus and technique described elsewhere.2'3 Six zone-melting passes were used to achieve a total impurity level of about 30 ppm. Of this 30 ppm, the combined nickel and cobalt content was about 20 ppm, oxygen was 4 ppm, and all oxidizable impurities less than 1 pprn each. A vertical resistance furnace wound with molybdenum wire was used for the experiments. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. In the gas train, flow rates of hydrogen and argon were measured with capillary flow meters, and the resulting mixtures were passed through a column containing 90 pct oxalic acid dihydrate and 10 pct anhydrous oxalic acid to obtain predetermined ratios of H2O to H2. The vapor pressure of H2O above this mixture as a function of temperature is well-known.4 The exit gas was ana- lyzed periodically for H2O, and good agreement (+3 pct) with the calculated composition was obtained. The zone-refined iron specimens were held in the furnace for a sufficient length of time for equilibration, e.g., 18 hr at 1350°C and 1 week at 881°C, then quenched in a brine solution. After removing the surface oxide from the samples by machining, duplicate analyses were obtained by a combined vacuum fusion-infrared method; oxygen analysis was reproducible within 2 ppm. Permeability Measurements. The permeability of oxygen in alloys containing about 0.1 pct A1 was determined by internal oxidation and measurement of the subscale thickness as a function of time. The experimental alloys were prepared by adding aluminum to electrolytic iron (grade 104A plastiron) that had previously been vacuum-carbon deoxidized. The resulting ingots contained about 20 ppm O, 100 pprn C, 40 pprn Si, 50 ppm Mo, 20 ppm P, 20 ppm S, and 20 pprn Zr as the principal impurities. After hot rolling the ingots to 1-in.-thick slabs, specimens were machined from the stock in the form of rectangular plates, 4 by 5 by 2 in. The general procedure for the permeability experiments was the same as those for the solubility measurements. The specimens were cooled in a reducing atmosphere rather than quenched, however, in order to maintain a clean surface for measurement of the sub-scale thickness. This measurement was made on a polished cross section of each specimen, using a microscope with a micrometer stage. The inclusions formed at the lowest temperature 1033°C were too small to be seen with an optical microscope. An electron micrograph showing the size and shape of individual particles is shown in Fig. 1. The dark band in the picture is a boundary between two subgrains. The subscale thickness in these samples was measured with an optical microscope after heavily etching in 2 pct nital, which gave contrast between the subscale and the unoxidized zone.

Jan 1, 1968

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 V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By Takeyasu Ito, Mayumi Someno, Kazuhiro Goto

SINCE the pioneering work by Kiukkola and Wagner,1 many experiments have been reported on solid electrochemistry at elevated temperatures. However, the studies have been confined to experiments under isothermal conditions. One may conceive many situations under nonisothermal conditions. With two different temperatures T1, and T2 at the two electrodes, the electromotive force, E of a Galvanic cell will be expressed by the following equation under a steady state heat transfer in solid electrolytes of zirconia-lime and thoria-lime. E = ^ $ l&-dGO2+a(T2-Ti) [1] where tO2- is the transference number of oxygen ions in the electrolyte, Go, is the chemical potential of oxygen, and a is the coefficient of the thermoelec-tromotive force due to the temperature difference. The objective of the present study was to evaluate the coefficient of the thermoelectromotive force for zirconia-lime and thoria-lime under isobaric condition. The physical meaning of this coefficient is out of the scope of the present communication. The experimental cell assembly is schematically shown in Fig. 1. The zirconia-lime electrolyte tube and thoria-lime electrolyte tube were 8.0 mm OD and 5.0 ID, from commercial sources with chemical analyses of 94.8 wt pct ZrO2, 3.85 pct CaO, 0.83 pct SiO2, 0.25 pct TiO2, and 0.05 pct Fe2O3; and 95.0 pct ThO2, 4.0 pct CaO and rare earth metal oxides, respectively. The specific gravity was 5.5 g per cu cm for zirconia-lime and 9.8 g per cu cm for thoria-lime. Original powder size before shaping and sintering the tube was several microns for both electrolytes. The distance separating the two electrodes was 4.0 or 5.0 cm. Platinum wire of 0.5 mm diam was used for the electrodes. The temperature gradient was controlled by heating one electrode with a small heating coil of nichrome wire. The temperatures at the two electrodes were measured with two calibrated Pt-13 pct Rh:Pt thermocouples, directly contacting the two platinum electrodes. The atmosphere was either air or pure oxygen. The partial pressure of oxygen in air was considered equal at the vicinities of the two electrodes, with negligibly small thermal segregation in the gas phase. The difference of the chemical potential of oxygen was controlled only by the temperature difference at the two electrodes and not by the oxygen pressure difference. The temperature ranges were 600" to 1200°C for zirconia-lime and 850" to 1200°C for thoria-lime electrolytes. Fig. 2 shows the relation of the measured electromotive force and the difference of the oxygen chemical potential at the two electrodes for zirconia-lime and thoria-lime electrolytes. The electromotive forces in the figure were measured by a *0.05 mv potentiometer. The chemical potential difference was calculated by the following equations.'

Jan 1, 1970

By G. D. Tranter

THE importance of ladle and teeming practice and its relationship to the yield and quality of the product has focused considerable attention on this phase of open-hearth operation. Inherently bad steel cannot be perfected by manipulation during teeming, but through the proper handling of "off heats" serious losses, which in many cases arise, can be greatly minimized. Conversely, good steel can be ruined as a result of poor workmanship in the pit, and rendered unsuitable for application to orders where exacting surface and physical requirements are essential. Sufficient evidence has been secured to warrant careful investigation of pit operations when an abnormal number of basic defects develop in the semifinished product or are found on the inspection table. This paper is written from the standpoint of the problems involved in making satisfactory ingots for sheet rolling. Furthermore, since rimming steel is almost universally used for manufacture of sheet, the data presented herein refer particularly to that type of steel. Going back some 30 years in open-hearth history, the word "pit" properly described the hole into which the ladle was lowered to receive the metal tapped from the furnace. The working space was necessarily limited, and the disposal of slag and metal overflowing the ladle or lost because of breakouts presented a serious problem. The equipment, of course, was rather crude in the light of present-day development. Often no ladle stands were provided, the ladle being hung on the crane beneath the runner. When delayed taps occurred, the ladle was often held in position for many hours, thus tying tip pit operations and causing delays to adjacent furnaces. Because of crowded conditions, slag thimbles were not used and a network of cast-steel triangles and old tapping bars, placed before the heat was tapped, was the means for removing slag from the hole. Furnaces of different capacities were used

Jan 1, 1935

By J. Leja, A. Pomianowski

This paper deals with equimolar solutions of xanthate and alkyl trimethyl ammonium bromide adsorption on copper, nickel and sphalerite powders. After an exposition of the experimental methods used and the results obtained, a thorough discussion leads to the conclusion that some molecular association between xanthates and CnTAB's does take place in the bulk of the solution as well as at the air/liquid interface. A spectrophotometric study of xanthate solutions alone and their mixtures with equimolar amounts of alkyl trimethyl ammonium bromide (CnTAB) has established the additivity of ultraviolet spectra (190 to 400 mµ) for potassium ethyl xanthate (KEtX) and C12TAB. No obvious effect of C12TAB addition on the decomposition rate of KEtX was observed, the half life of which was established as 29±3 days at 22°C and pH ~ 6. In mixed solutions of longer xanthate homologues (e.g. hexyl and nonyl) and equimolar CnTAB, colloidal precipitates are gradually formed which contain primarily the corresponding xanthate molecules. The kinetics of collector abstraction by copper, nickel and sphalerite powders were studied in 10-5 to 10"3 M solutions of KEtX alone and in equimolar mixtures of KEtX and CI2TAB. Presence of C12TAB caused a two to three fold increase in the amounts of xanthate (equivalent to many monolayers) abstracted by copper and nickel powders (and in their rates of abstraction) but had no effect on the abstraction of xanthate by unactivated sphalerite (equivalent to less than a monolayer). The adsorption of C12TAB itself from the mixed solutions was very low, at most one monolayer only, and was not influenced by the nature of the solid powder used. A change in the rates of abstraction, observed with copper powder, was interpreted as a completion of a multilayer coating (completely enveloping the grains of powder) following which the rate of reaction between solution and substrate becomes controlled by diffusion through this coating. Work of Buckenham and Schulmanl on molecular associations between different collectors has shown unusual synergistic effects in flotation of individual minerals using mixtures of xanthates and alkyl trimethyl ammonium bromides. The objectives of the present work were: 1) to determine whether these molecular associations between the two types of collectors (indicated by strong surface tension lowering in Buckenham and Schulman's work) take place at the air/liquid interface only or in the bulk of solution as well 2) to establish whether different solids adsorb any species from the mixture of these amphipatic molecules preferentially or as molecular complexes 3) to establish whether there are any differences in the kinetics of adsorption. Metallic copper and sphalerite powder were chosen as adsorbents since they represent two extremes since copper readily adsorbs multilayers of xanthate (and is easily floated with ethyl xanthate) while unactivated sphalerite does not appreciably adsorb xanthate but is known to be readily floated by the amine type collectors. Metallic nickel was included because the infrared spectroscopic work2 on xanthate

Jan 1, 1964

By F. E. Bash

CONSTANTAN is an alloy of copper and nickel that is extensively used, under a number of trade names, as a resistance wire with a low temperature coefficient of resistance, and one of the elements of base-metal thermocouples, iron usually being the other thermoelement, although for low-temperature work copper is also used. Before the war, constantan was imported, in common with many other technical necessities. Since it required considerable time to receive the constantan after it was ordered, fairly large stocks were kept on hand; but after the beginning of the war no more was imported acid the stocks of foreign material were exhausted about the same time that the steel and munition manufacturers began to need great quantities of it for thermocouples for the heat treatment of steel. To meet this demand, the International Nickel Co. began manufacturing constantan that met all the requirements of the users of resistance wire but did not give the same electromotive force against iron as the German material and consequently could not be used with instruments calibrated for a definite e.m.f.-temperature relation. It so happened that all the constantan made had an e.m.f. lower than that necessary to meet the specifications of the Leeds & Northrup Co. for whom this investigation was carried out. If some had been higher and some lower, good wire could have been obtained by a, process of selection, but as it was no wire at all could be procured. To remedy this situation, a thorough investigation was started with the close cooperation of the International Nickel Co. and the Electrical Alloys Co. The specifications to which the constantan had to conform were that it should give an e.m.f. of 47.40 millivolts. against pure iron at 1500° F. (816° C.) with the cold-junction temperature at 0° F., or a proportional e.m.f. at temperatures near 1500° F. The method of checking a wire was as follows: It was first welded to a piece of iron wire; Armco iron was found to be satisfactory but iron with greater than 0.1 per cent. carbon would give a lower e.m.f. against the same piece of constantan than pure

Jan 9, 1919

THERE can be little doubt in the mind of anyone of the great interest which has been provoked in the mining and petroleum industry by the com-paratively new geophysical methods of prospecting, after the sessions at this year's meeting of the Institute. Not only were the sessions very well attended but every¬one seemed most attentive. Although the discussion was somewhat limited in general, that may well be at-tributed to the newness of the subject. Two sessions on this subject were planned originally, but these gave insufficient time for the presentation of all the papers prepared and a third session was abso-lutely necessary. The first meeting dealt entirely with the gravity methods and was completed in the scheduled time owing to the fact that but two of the five papers listed were read. The second session was devoted to magnetic and electrical methods, the completion of which had to be carried over into the third period of geophysics. The first session on geophysical prospecting, and in-cidentally the first scheduled Institute meeting devoted entirely to this subject, was most appropriately opened by E. L. DeGolyer, the chairman of the session. It was through the efforts of Mr. DeGolyer that the first gravity work, as applied to prospecting, was under-taken in this country. Again most appropriately, the first paper presented was given by Donald C. Barton, who carried on the first work with the Eötvös torsion balance in America and aided materially in its development. A subject, the theory of which is so difficult to understand as it is generally presented, was so clearly illustrated and ex-plained by the speaker that even a novice could grasp the fundamentals. Dr. Barton, in showing actual re-sults obtained in torsion balance surveys with the in-terpretation of the sane and later drilling records, was free in stating that there are many limitations to the field in which this and the other geophysical instruments may be successfully employed. This paper called for considerable discussion relative to the application of the torsion balance to gravity surveys over various types of structures. During the course of this discus-sion a very important point was emphasized by the chairman, namely, that for successful application of any or all of the scientific methods of prospecting, a back-ground of experience is absolutely necessary to serve as a basis for further work. This can only be secured by contributions from the results of actual prospecting work.

Jan 3, 1928

By Newell Hamilton

Some years ago, in the manufacture of seamless tubing from an alloy steel containing 0.07 per cent maximum carbon, 18 per cent chromium and 8 per cent nickel, at the plant of The Babcock & Wilcox Tube Co., a peculiar type of piercing defect was noticed. This defect was definitely associated with certain heats of the alloy and was independent of any of the variables of mill operation and billet-heating condition. A thorough analysis of the defective material yielded but one clue to the reason for its abnormal behavior in piercing and that was its oxygen content as determined by the vacuum fusion method. The oxygen content of the defective 18-8 alloy was found to be from two to three times that of the material that had pierced satisfactorily, and this incited an active interest in the vacuum fusion method for the analysis of alloy steels. After a critical survey of the literature on this subject, and considerable experimentation, an apparatus and technique were evolved that gave a fairly rapid, simple and reliable method of analysis. Samples selected from six years of tube production of 18-8 and other corrosion-resistant alloys were analyzed by this method. This paper describes the procedure and gives a correlation of the oxygen, hydrogen and nitrogen contents of a number of alloy steel samples representative of good and bad tube-piercing quality. The Apparatus Basically the apparatus used in this work was that of Jordan and Eckman,' employing a high-frequency induction furnace and the gravimetric method of analyzing the evolved gases, nitrogen being excluded from the determination. In addition, a magazine-type cap and a large-

Jan 1, 1934

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946