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Jan 1, 1939

By Gerhard Derge, Harold Markus

The introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be dcscribed. For most of the additions, solutions containing 0.001 and 0.01 moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-l,ol~ate as follows: pH 0.1 M NaHC0............................................ 8.4 2 parts 0.1 M XaHCOr, 1 pa.rt 0.1 M NaZCO?................. 9.5 1 part 0.1 M NaHCOs, 2 parts 0.1 M iVa.,C03. ................ 10.0 0.1 M Na2C0............................................. 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves—sulphnte, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only -fuoridc, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also—phosphate, pcrborate, and chromate. Potential Measurements f The time-potential curves represntative of group 1 are shown in Fig. 1. These are the curves for 0.005 M sulphate ion and their similarity

Jan 1, 1939

By C. W. Macgregor

The observation of the flow layers, or Luders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-st'eel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are ill reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45" to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ncr, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45" to the principal stress direct-tions at the point. As examples of the latter may be mentionecl the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subject,ed to internal pressure only, etc. IIencc if the flow layers are observed from an experiment, the shear-st'ress trajectories —the curves indicating the direct,ions of the maximum shearing stresses in the body—may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45" to the principal stress directions, the family of principal stress trajectories, or the curves irldicating the directions of the principal stresses, may be thus obtained Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowai~; in duralumin and other aluminum alloys, by Dawidenkow,~Elam,~ Fell4 an(l others; in copper and copper-alloy crystals, by Elam;~ in brass by Elam;3 in brass wires by deForest;" in higher carbon steels, tungsten steel, and

Jan 1, 1939

By L. L. Swift

.It the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical, duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows ill sorne types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing tuetal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cicnt of friction. Under most operating conditions the friction depends on the unit, pressure of the bcaring, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.' The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measurement of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual canstituents was developed to fill this need. MICROCHARACTER The Bierbaum MicroCharacter~,~ measures the scratch-hardness of a solid by pulling a weighted diamond point over the surface. The diamond point is ground so that it is the corner of a cube, and Mounted

Jan 1, 1939

By W. D. Forgeng, D. Beregekoff

In the routine examinatlion of a wide variety of metal specimens it is sometimes necessary to have special methods of polishing in order to retain and reveal certain details in each specimen. Among such special cases is the retention of graphite in malleable and gray cast irons, the preservation of all types of non metallic inclusions in both hard and soft steels, obtaining a scratch-frec surface with soft metals, and avoiding the usual relief effects with very hard specimen. such as tool metals c3o1ltaining various carbide and nitride phases. It, is the purpose of this paper to give an account of some of these special polishing methods in use at the Union Carbide and Carbon Research Laboratories. The polishing procedures outlined have been found to give uniform results. It is obvious that only general rules and the most important working details can be given here. Following these rules, the polisher can obtain satisfactory results if he possesses the necessary patience and has a sincere desire to give as nearly perfect a finish as possible to his work. Procedure The specimen is flattened with considerablecare on a file or sharp cutting sanding belt, since the initial production of a flat surfacc greatly facilitatcs subscqucnt polishing. The polishing motors have two speed., 600 and 1200 r.p.111. ,It higher speeds specimens arc likely to he over-Ileated, therefore the high speed is used only when a saving of time is important. The following abrasive papers are used consecutively: Yo. 2, So. 1, No. 0, No. 00 and No. 000. The final wet polishing is done oil a cloth-covercd metal disk. Woolen broadcloth of the best quality and capable of resisting severe pressure is most commonly used on the last lap. . polishing felt of the type used for polishing optical glass has been found equally satisfactory and is much stronger than broadcloth. For retaining inclusions and graphite, a hard cloth with very little residence, such as

Jan 1, 1939

Jan 1, 1939

Some Things We Don't Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

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Jan 1, 1939

By Alwyn Birchmore Cox, Ian William Wark

Sodium sulfide is used extensively to increase the recovery of oxidized copper and lead minerals by flotation, particularly when using xanthates as collectors. It is generally assumed that the sodium sulfide converts a film of the oxidized mineral to the sulfide, and that the xanthate, while not a very effective collector for the oxidized minerals, is a good collector for the sulfide. On the other hand, Taggart and his collaborators1 claim that unless sulfide minerals are oxidized they cannot adsorb xanthates and do not float. Gaudin2 states that amyl xanthate, used in conjunction with sodium sulfide, gives better results than ethyl xanthate. Rabone3 and Mayer-Schranz4 agree that excess of sulfide functions as a depressant. Owing to the greater solubilities of the oxidized minerals than of the sulfides, the consumption of sodium sulfide is greater than that of most other flotation reagents, up to 10 lb. per ton of ore being used in some plants. Luyken and Bierbrauer5 recommend a water washing to remove soluble heavy metal salts; by this means sulfide consumption may be reduced. It was desirable to determine the limits of the sulfide concentrations between which contact is possible at surfaces of anglesite and cerussite in xanthate solutions. Similar determinations were desirable for the sulfide minerals with which the oxidized minerals are usually associated, since conditions should be chosen, if possible, so that the two types of mineral will float together. Because of the formation, especially in acid solutions, of hydrogen sulfide and of the hydrosulfide ion (HS-), the permissible limits of sulfide addition are obviously dependent upon the pH value. Sphalerite responds to ethyl xanthate only in the presence of an activator; for example, copper sulfate. It was necessary, therefore, to determine whether sodium sulfide interferes with the activation of sphalerite by copper sulfate. The combined effect of sulfide and copper sulfate was determined also for galena, chalcopyrite and pyrite.

Jan 1, 1939

By Alwyn Birchmore Cox, Ian William Wark

In defending the chemical theory of flotation, Taggart, del Giudice and Ziehl have criticized1 the views of those who prefer to attribute the effects of certain flotation agents to adsorption. Perhaps with some justification, they describe the latter term as the "haven of refuge of writers lost in a morass of shaky experiment and muddy thinking." We prefer to regard it, however, as a haven of refuge for writers who seek a conventional term to describe the formation of films of flotation reagents on solid surfaces, because in many cases it is not yet possible to specify the forces that hold them there. Originally, as Taggart and his associates state, adsorption connoted a concentration difference and nothing more. In recent years, workers in the field of surface chemistry have tacitly added other meanings, and they now speak of orientated adsorption of unimolecular films on a solid sub-strate, of chemi-adsorption, and of exchange adsorption. Thus the term adsorption may connote simply the Gibbs layer of excess concentration at the surface of a solution, or a unimolecular film at the surface of a solid. Perhaps this has led to the misunderstanding of Taggart, del Giudice and Ziehl concerning the relationship between surface tension and adsorption at solid surfaces. The change in "surface tension" accompanying adsorption at a liquid surface can be used as a measure of the adsorption, and the Gibbs equation as quoted by these authors correlates these two conceptions. But, to correlate two conceptions docs not necessarily imply an attempt to explain either, although sometimes such an "explanation" is carelessly inferred. Use of "surface energy per unit area" instead of the numerically equal but more difficult and less definite conception of "surface tension per unit length " would lessen many of the present difficulties. (Compare with Adam.2) At interfaces involving a solid phase, neither '" surface tension " nor " interfacial tension "can have any meaning, but the conception "interfacial energy per unit area" call be understood by anyone who is familiar with the concept of free energy. While it is true that surface energy cannot be directly measured at a solid surface,

Jan 1, 1939

By Alwyn Birchmore Cox, Ian William Wark

Different parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. Experimental Method The methods used have been described previously.l-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1939

By Keith Leonard Sutherland, Ian William Wark

Mercaptobenzthiazole and its sodium salt are marketed under the trade names Flotagen and Flotagen S respectively, for use as collectors for cerussite and other minerals. The structural formulas for sodium rnercaptobenzthiazole and for sodium ethyl xanthate are: Chemically there is a resemblance between the two compounds, though the free acid (mercaptobenzthiazole itself) is much more stable than xanthic acid. Both are readily oxidized, e.g., by iodine to disulphides, and can be estimated by iodometric titration. Qualitatively they are similar as collectors in flotation, although there are quantitative differences between them that may be important in practice. It is deduced that the influence of the nitrogen atom is subordinated to that of the sulphur atoms, and that the dominant group of these compounds is the mercapto group —SH or —5Na. The general method of investigation has been based on contact tests. Two temperatures, 10" and 35" C., have been chosen, and with a standard concentration of 20 mg. per liter of mercaptobenzthiazole (i.e., of the free acid) the influence of alkali, cyanide and copper sulphate on contact at sulphide mineral surfaces has been studied. This standard concentration corresponds to about 19 mg. per liter potassium ethyl xanthate; it brings out the differences between the minerals better than a higher concentra-

Jan 1, 1939

By Oliver C. Ralston, James E. Norman

Separation of minerals by froth flotation is rightly called an art. It can truthfully be said that no two ores separate in the same way. The difference in results obtained when natural and synthetic mixtures of minerals are separated is so great that such tests frequently have been worthless in attempting to select conditions in which a natural mixture will separate. With a few rare exceptions, the natural mixture is much more difficult to treat than a synthetic mixture, and a much poorer separation is obtained. Perhaps several experimenters have wondered why 10 or 20 per cent of a mineral being floated from an ore does not float and is different from the 90 or 80 per cent that is recovered. In experimental tests on pure sphalerite, observers' have noted that varying amounts of sphalerite may be froth-floated with pine oil alone, the amount recovered in the froth depending apparently upon the source of the sulphide. The only explanation of results such as these, barring insufficiency of frother or time of flotation, is that the surface of the mineral floated is different from that of the mineral depressed. This difference often has been found to be caused by natural contamination of mineral surfaces, apparently brought about by weathering and exposure to natural solutions. There is virtually no rock that is absolutely unweathered. One of the writers had an exceedingly instructive experience in 1931 while working with United Verde copper-zinc iron sulphide ore in Arizona. Nonselective flotation of chalcopyrite and sphalerite away from some of the pyrite was all that could be accomplished. All known depressants produced only slight effect. Sodium cyanide showed some effect, but so much had to be used that only a small amount of chalcopyrite could be

Jan 1, 1939

By A. B. Hersberger, R. S. Dean

Although it is obvious that in any flotation process we must have a froth, in recent years the development of collecting reagents has caused the possibilities of better frothing agents to be overlooked. Some investigators have even gone so far as to say that the number of satisfactory frothing agents was sufficient. A little consideration will show, however, that the reagents available in the past were far from ideal frothers. The properties of an ideal frother for flotation work may be set down as follows: 1. It must form in low concentrations a copious but not too persistent froth. 2. It must be insensitive to hydrogen-ion concentration of the pulp; that is, it must froth equally well in an acid or alkaline medium. 3. It must be insensitive to salts, even in high concentration. 4. It must be absolutely noncollecting to both sulfides and nonsulfides. 5. Its frothing properties must not be affected by collecting reagents, including soap, the most generally used nonsulfide collector. 6. It must readily emulsify and disperse any insoluble collecting agent that is likely to be used. Clearly the existing frothers do not qualify. Pine oil, for example, is an acceptable frother for many purposes but if used in soap flotation a delicate balance between pine oil and soap must be struck because, as pointed out by Coghill1, these two reagents are incompatible in certain concentrations. The objections to soap itself as a frother are obvious, and the cresols and their substitution products all have some collecting power and very little emulsifying power. The mechanism of frothing in flotation was early explained on the basis of the Harkins-Langmuir theory of oriented molecules.2 These investigators showed that if an organic compound having an unsym-metrical molecule (in which one end of the molecule contained water-

Jan 1, 1939

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The high-frequency laboratory induction furnace with a rotating liquid crucible enables research workers to conduct certain investigations heretofore very difficult or impossible to realize because vessels are not obtainable that are capable of resisting the physical conditions or the chemical actions to which they are subjected. Applications for patents covering commercial uses of centrifugal liquid crucibles were filed in the United States in 1919,' in France in 1925, in the United States and Germany in 1926,2 and in France in 1927.3 In 1928, Schuette and Maier,4 of the Bureau of Mines, reported the construction of a whirling table beneath a high-frequency induction furnace. Shape and Size of Centrifugal Liquid Crucibles When a vessel containing a liquid is rotated, the inner surface of the liquid takes the shape of a paraboloid under the simultaneous action of centrifugal force and gravity. The internal dimensions of the paraboloid rotating liquid crucible are governed by the diameter of the container and its speed of rotation. Melted Wood's metal was poured into cylinders 2 1/2 in. in diameter, which were rotated at 180, 300, and 468 r.p.m. When the metal was solid, a slurry of plaster of Paris was added, and rotation continued until the plaster had set. Fig. 1, a photograph of sections of the cylinders, shows the effect of speed of rotation of the containers upon the shape of the inner surface of the rotating liquid crucibles. Types of Furnaces Three types of high-frequency induction laboratory furnaces using liquid-metal crucibles were designed and constructed by the Blast

Jan 1, 1939

By Anson Hayes, John Chipman

The quality of sheet and strip products made of rimming steel is closely related to the structure and chemistry of the ingots. The variation in composition throughout the ingot, as affected by segregation, is of great importance, as are also the form and distribution of the voids that result from the gases evolved. It is because of this importance that the considerable literature in this field has accumulated. No attempt is made in the present paper to compile a bibliography of the excellent work that has already been done, as this has been adequately covered in the many excellent reports on the heterogeneity of steel ingots prepared by a joint committee and published by the Iron and Steel Institute.' From time to time, in any field of investigation new tools and new technique are developed, which make further progress possible. In the field with which this paper is concerned, this is true. The development of the vacuum-fusion method as a means of following oxygen segregation, and a technique for obtaining the volume and composition of the gases evolved during solidification, have opened the way to obtaining data by means of which some considerable progress has been realized in developing more of the detailed mechanisms of solidification and segregation in rimming-steel ingots. General Theory of Segregation The basic cause of segregation lies in the fact that the impurities are less soluble in solid than in liquid iron. The solid that forms from the impure liquid is more nearly pure than the liquid itself. If solidification proceeds slowly enough, or if the liquid and solid phases are maintained in contact with one another for a sufficient time, a condition of equilibrium is set up, which may be represented by a phase diagram. Portions of the

Jan 1, 1939

By A. Hultgren, G. Phragmén

Page Outline of Progress of Knowledge and Theories about Gas Evolution in Steel Ingots. and Its Influence on Crystallization and Segregation................ 134 Object of Present Investigation........................................... 148 Theoretical Discussion of Process of Solidification........................... 149 Gas Given Off from Rimming Steel during Solidification................... 149 Equilibrium Diagram of the Iron-carbon-oxygen Alloys................... 151 Solidification of Pure Iron-carbon-oxygen Alloys.......................... 157 Solidification when Carbon Monoxide Is Given Off at Constant Pressure... 157 Solidification when Gas Evolution Is Suppressed....................... 158 Schematic Application on Solidification of Rimming-steel Ingots.......... 159 Influence of Manganese, Sulphur and Phosphorus......................... 160 Experimental work..................................................... 162 Liquid Steel and the Mold Gas......................................... 162 Ingots Investigated and Methods Used.................................. 165 Ingot structure....................................................... 174 Structure of Rim Zone.............................................. 174 Structure of Core................................................... 181 Structures Obtained under Special Conditions of Freezing................ 182 Distribution of Metalloids............................................. 187 Other Observations Made............................................. 192 General Discussion of Solidification Process................................. 195 Condition of Liquid Steel before Casting................................. 195 Rimming Period...................................................... 202 Composition of Rim Zone............................................. 225 Freezing after Top Is Closed........................................... 228 Slag Inclusions and Ingot Scum........................................ 234 Reaction between Gas in Blowholes and Surrounding Solid Steel during Cooling 235 Summary.............................................................. 237 Appendix—Preparation and Etching of Ingot Sections....................... 238 References............................................................. 239 In 1934, Jernkontoret (The Swedish Ironmasters' Association) appointed a committee for the study of the structure of rimming-steel ingots and the various phenomena associated with their solidification. The members of the committee, including those who have joined it later, have been: I. Bohm, B. D. Enlund, B. Kalling, M. Tigerschiöld, S. Wohlfahrt and the authors. The present paper‡ is a somewhat

Jan 1, 1939