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By Clarence Zener

Contents Page General Principles................................................................. 551 Equilibrium Diagrams......................................................... 551 Nucleation................................................................... 553 Kinetics of Phase-boundary Propagation......................................... 553 Kinetics of Growth of New Phase............................................... 556 Spheroidization............................................................... 560 Pure Iron-carbon System........................................................... 561 Formation of Pearlite.......................................................... 561 Interlamellar Spacing........................................................ 562 Pearlite C-curve............................................................. 563 Bainite Formation............................................................. 565 Formation of Martensite....................................................... 570 Loss of Tetragonality of Martensite.............................................. 570 Effect of Alloys upon Decomposition of Austenite..................................... 572 Pearlite...................................................................... 572 Bainite and Martensite......................................................... 574 Time-temperature-transformation Curves............................................. 576 Appendix A............................................................. ......... 579 Appendix B....................................................................... 580 Appendix C....................................................................... 580 The present investigation started in an attempt to understand certain details of the decomposition of austenite, and of the effect of alloying elements thereon. As the investigation proceeded it became apparent that not only these details, but all the general features of austenite decomposition, could be understood in terms of fundamental physical principles. Since the direct applicability of these physical principles has not been previously recognized, it was decided to incorporate the original results of the investigation into a review of the general subject of the kinetics of austenite decomposition. This review constitutes the present article. An extended summary of the results is given on pages 576 to 579. This article, which deals with the kinetics of phase transformations, may appropriately be considered as a sequel to two recent articles1,2 from this laboratory on the equilibrium relations in medium alloy steels.

Jan 1, 1947

By P. D. P. Hamilton

In any mining district where benefication of the ores is practiced, one can usually observe several types of flow sheets even though the various producers are milling ore from the same geological formations. It is obviously impossible to describe all the mills in the Porcupine district. However, the following description of some of them is of particular interest in that it shows where one mill has paid particular attention to corduroy blanket practice; one to gravity concentration of sulfides for intensive cyanidation of the values therein contained; one to flotation of values and cyanidation of this product only; and others where small variations of standard all-slime cyanidation practice prevail. In all cases it will be seen that cyanidation is the basic principle. Discussions involving the difference in the flow sheets and the reasons for them will always be of value to those interested in the art. The author of this article, however, believes that such discussions should originate from the operators of the mills under discussion. For this reason no comparisons or discussion will be included in the description of the mills mentioned. Should any reader of this article obtain information therefrom which will be of value to him in helping to solve his own particular problems, the author will consider that the article has satisfactorily served its purpose. All values mentioned throughout this article are based on the value of gold at $20.67 per ounce. Coniaurum Mines, Limited The ore of the Coniaurium mines consists of a mineralized schist and quartz containing about 2.5 per cent sulfides. Owing to the low grade of ore developed in the mine, extreme care has had to be exercised throughout the entire mining and milling operation in order that an operating profit might be obtained. The management, however, has been able to keep costs down, with the result that at present the outlook for the property is considerably brighter than it has been in the past. This is partly due to the fact that it is now known how to mine and treat

Jan 1, 1935

By H. Kreye, E. Hornbogen

An increase in electrical resistivity during aging or after quenching from high temperatures is known in a large number of alloys. Plastic deformation of alloys in this condition leads to a decrease in resistivity. This anomaly has been called the K effect. This effect has been reported in Ni-A1 alloys by several authors.'-4 The nickel-rich solid solution y is in equilibrium with Ni,A1 (y') with CkAu structure. With this alloy it is therefore possible to produce a homogeneous solid solution as well as a coherent mixture of y and y. The changes in resistivity should be determined for these two conditions. In the present literature on the K effect no distinction is made between them, because of experimental difficulties to determine small coherent particles. In the present work transmission electron microscopy and image formation by (100) and (110) superlattice reflection of the y' phase was employed for a detailed determination of the temperature dependence of solubility of aluminum in nickel and the resulting microstructures with alloys up to 15 at. pct Al. The solubility line follows the equation indicating a smaller solubility than given in the literature at temperatures below 700°C. X-ray scattering was used to get evidence for short-range ordering in the homogeneous solid solutions.5 Parallel to the determination of the microstructure electrical resistivity was measured as a function of aging tempera- ture, time, and aluminum content, which led to the following results: 1) Resistivity increases slightly during aging of a homogeneous solid solution which was quenched from a high temperature as a consequence of short-range order, Fig. 1, curve c,. 2) Resistivity shows a maximum during aging of all alloys which are heterogeneous according to the phase diagram, but which were obtained as a supersaturated solid solution by quenching, Fig. 1, curve c,. The increase in resistivity is mainly due to coherent precipitation of y'. In Fig. 2 the effects due to short-range order pN and due to precipitation of particles APT are shown for an aging temperature of 450°C and different aluminum contents. 3) The increase in resistivity depends on the size !f the coherent particles. A critical diameter of 15 5A for the maximum was found for all alloys and aging treatments by extrapolating particle sizes determined by electron microscopy. 4) The maximum of resistivity of the heterogeneous conditions does not occur if particles, larger than the critical size, have formed already during quenching. 5) Plastic deformation destroys short-range order as well as small coherent particles. Therefore a decrease in resistivity is observed if the increase in resistivity caused originally by these phenomena is

Jan 1, 1967

By Jerome Alexander

The object of this paper is to show that many of the important phenomena of metals and alloys are due to the facts that, at some stage, metals and alloys, or some of their constituents, are in a colloidal state and that a portion of the metal or alloy tends to remain in this state. The so-called amorphous phase in pure metals is an isocolloid, consisting of colloidal groups of metal molecules that may be dispersed in still more finely subdivided metal; these colloidal particles are not truly amorphous, but may consist, in part, if not entirely, of ultramicroscopic crystals; as a result the expressions amorphous phase and amorphous theory might he replaced by the expressions colloidal phase and colloidal theory. Any substance is in the colloidal state when the constituent particles consist of molecular or atomic groups, whose size varies approximately from about 100 down to about 5pp, that is from just below the limit of microscopic resolvability to the dimensions commonly ascribed to the larger molecules. Colloidality involves no assumption as to the shape, internal structure, or orientation of the colloidal particles; size alone is the critical factor. A colloidal system may therefore contain crystalline groups, or amorphous groups (non-crystalline, random or haphazard clusters), or a mixture of the two. All colloids consist of at least two phases, the subdivided substance, or dispersed phase, and the substance into which this is subdivided, the dispersion medium. It is not necessary that there be any chemical difference between the dispersed phase and the dispersion medium. As molecular forces are extremely powerful, their application may produce marked changes in the physical properties of metals. It is doubtful whether metal in the interior, especially of large masses, possesses the same properties as that on or near the surface, which alone is open to inspection.

Jan 1, 1921

JOHN W. BELL (communication to the Secretary*).-I have to thank Mr. Merrill not only for his very kind remarks, but for the weight of his implied opinion that the work accomplished probably has an important practical aspect. I think there is a distinct although unuttered impression among engineers, that it will be time enough for them to begin to take an interest in the law of crushing when it emerges from the cloud of violent and even vituperative controversy that has hovered over it during the last 6 or 7 years. I have a very confident feeling that as the result of the work done by Mr. Gates, by me and by Messrs. Mitchell, Baily and Cockfield, who so loyally helped me to obtain the necessary data, at least the practical law of crushing has emerged; that it is ready and available for use by our fellow engineers, and that it will help them to unravel a number of the many practical problems they are con¬stantly confronted with. In regard to Mr. Gates' discussion, I would indeed like to believe that McGill could claim, as a minor achievement, the credit which Mr. Gates so generously bestows of having established the "law" of crushing. I think that more work would be required to establish this claim in the, strict sense of the word, as there is a fairly large gap between the coarse and fine crushing results. I am not worried about that gap, because the reason for it is quite clear to me; at the same time I-think it will be well to bridge it by a series of tests, and I am bound to admit that the testing machine is the most promising machine right at hand to work with, although whether the minute amounts of power required to crush small quantities of rock can be so accurately integrated as to insure high accuracy in the final result is still a question in my mind. If we had an Amsler-Laffon machine I would certainly try it. Mr. Gates' remarks about choke crushing are extremely interesting. He compels me to wonder, too. It is a new and probably a very important factor to be considered in this connection. I am in perfect accord with Mr. Gates about the desirability of the determination of crushing constants, because when this is accomplished the efficiencies (not relative mechanical, but real efficiencies) of different types of rock-crushing plants in any part of the world will then be comparable. For this reason it would, seem desirable that the American Institute Committee should not only consider ways and means for accom-

Jan 6, 1917

By David R. Maneval, Jack M. Campbell

The regulatory process by which governmental authorities acknowledge and, in turn, permit the location, construction, and operation of large scale energy-related facilities has become extremely detailed in recent years. One example of the detail that is entailed in the regulatory process is the number of permits that must be acquired by operators prior to the construction and operation of energy-related facilities. It has been estimated, for example, that 75 permits are required prior to the opening of a new coal mine in Pennsylvania while 50 are required in Kentucky. From the perspective of facility owners and operators the regulatory process often appears overly complex and may be perceived as a constraint to the corporate decision making process. From the perspective of those responsible for administering regulations, the process is perceived as a means by which public desires-pursuant to social objectives such as environmental protection and occupational safety-can be achieved. As a result of conflicting organizational interests, the clash between energy facility owners and operators and their regulators appears to be inevitable. Furthermore, the resolution of this conflict lies in the trade-off between objectives and the costs of regulation. The balance of objectives and costs is a subject of the political process and not a topic of consideration in this paper. This paper is concerned with the actual administration of regulations, that is, the implementation of that which arises from the interplay of organizational interests. The paper assumes that environmental control laws will not likely be repealed, that regulations to implement the intent of these laws are here to stay and thus the paper seeks to assess how regulations are administered at various levels of government pursuant to objectives. The paper hypothesizes that the administration of objectives (or policy) has an impact on decision making which affects energy facility decision making. While recognizing the fact that regulatory policy cannot be totally divorced from administration, this paper proceeds under the assumption that elements of the regulatory process may be examined individually. The subject of this study is limited to the interplay between regulatory agencies and their clientele.

Jan 1, 1979

By D. J. Blickwede

PRESENT knowledge of the effects of time and temperature upon stabilization of the austenite-martensite reaction in steel is fairly complete,1-3 but at the time the work described herein was initiated there was no information about the effects of alloy elements on the phenomenon. However, it has been assumed on theoretical grounds that alloy elements, particularly carbide formers, may have a significant effect on stabilization.' The present work was undertaken to provide information about the effect of two common elements, nickel and molybdenum, on stabilization in hypereutectoid and hypoeutectoid steels. Seven induction-furnace melted, 1.2 pct C steels ' with a variation of nickel from 0 to 6 pct and of molybdenum from 0 to 1.0 pct were used for most of the experiments. Along with these a series of 0.4 pct C steels containing 0 to 6 pct Ni were also studied. The chemical compositions of the steels are listed in Table I. Stabilization in these forged, hot-rolled, annealed, and centerless ground steels was measured by aging brine-quenched specimens (aus-tenite temperature, 1800°F) at 95" and 150°F and then determining the change in specific volume produced by subsequent cooling from room temperature to —320°F.³ In presenting the results the decrease in the change in specific volume, ?V, after various stabilization times is used. This is given by ?V -= ?VO - ?V1 where AVO is the change in specific volume on quenching directly to —320°F and aV, is the change in specific volume on quenching to —320°F after stabilizing for time t. In other words, ?V is a direct measure of the amount of martensite that is lost to the subzero quench as a result of stabilization and hence is greater, the longer the aging time or the higher the aging temperature. The results are shown in Fig. 1. The scatter of the data, which are not shown for clarity and brevity, was sufficient to make the relative location of the curves on the ?V axis inaccurate within ±2x10-5 cc per g. However, some generalities appear which are of interest. Effect of Nickel In the 0.4 pct C steels, up to 3 pct Ni has little, if any, effect on the rate or amount of austenite stabilized at 95°F, Fig. la. Increasing nickel from 3 to 6 pct almost doubles the amount of austenite stabilized in a given time. In the 1.2 pct C steels aged at 95°F, increasing the nickel from 1 to 3 pct appears to decrease the amount of stabilization, and a further increase to 6 pct Ni completely eliminates stabilization as shown in Fig. lb (M, of 6 pct Ni steel was below room temperature). The same behavior was exhibited by these steels stabilized at 1500°F, especially after aging for periods longer than 5 hr, Fig. lc. Thus it appears that up to 1 pct Ni has little effect on stabilization at low or high carbon levels. More than 1 pct Ni increases stabilization at low carbon contents and decreases it at high carbon contents. Ward, Jepson, and Rait5 have found that at inter-

Jan 1, 1954

By Howard Talbot

THE history of the development of the strip in- dustry, mentioned in this paper, was covered in considerable detail by Stephen Badlam in his paper presented. before the American Iron and Steel Institute at its meeting in New York last October. The description of progress in rolling strip there out-lined will be found good reading by anyone interested in the subject. Quoting from Mr. Badlam's paper, "For practically thirty years, we find no record of the use of the backing-roll principle, until in 1916 the Lukens Steel Co., Coatesville, Pa., put in a 206-in. plate mill of the four-high type. This was a reversing mill with two 32-in. working rolls and two 50-in. backing rolls and is today making the widest and heaviest plate made anywhere in the world." The functioning of this mill, though rolling hot plate, is, on account of the extreme width and thinness of plate rolled, quite comparable to the rolling of wide strip either hot or cold and was a considerable factor in demonstrating the marked advantages available with the four-high or backing-roll mill for thin accurate rolling. As the writer has brought out, a demand for a product, the rolling of which required the character-istics of the backing-roll mill, was broached by the In-ternational Nickel Co. This resulted in an inquiry of March, 1924, for the building of a mill capable of cold-rolling wide nickel and monel metal sheets or strip, as mentioned. It may be of some interest to note, that whereas the .six-roll cluster mill with plain bearings was built for this installation, the mill designed by the United En-gineering and Foundry Co. for this inquiry was of the four-high type with roller bearings on the backing-roll necks, being essentially the same design as the four-high roller-bearing mill built in 1925 for the Rome Brass & Copper Co. This Rome mill, to quote again from Mr. Badlam's paper, "fulfilled every requirement, and was the model on which succeeding mills of this type were built."

Jan 5, 1928

By John H. Hollomon

The interpretation of notched-bar impact results has been a matter of controversy since the introduction of more or less standard tests by Fremont,' Charpy2 and others at the turn of the century. Many investigators3-l1 have contributed to the understanding of the significance of such tests. Several symposiums12,13 have been held with the express purpose of discussing the significance and interpretation of the impact tests. It is not the purpose of this paper to review all these contributions to the development of the knowledge on this subject, but rather to present an interpretation of notched-bar impact tests that appears to be in agreement with the available published data. Fundamentally, the interpretation discussed in this paper of the brittle failure of some steels in notched-bar impact test is similar to the qualitative analysis presented by Ludwik3 in the I92o's. Essentially, Ludwik stated that the function of the notch was to increase the tensile stress necessary for yielding, and that brittle failure occurred when the stress necessary for yielding exceeded the normal stress required for fracture (with no plastic deformation). Ludwik, however, had no means of measuring this normal stress necessary for failure of a plastically* undeformed metal, therefore he could not extend his interpretation beyond the qualitative stage. Kuntze14 and recently Mc-Adam15 attempted to determine the effect of deformation on the stress necessary for fracture by testing, in tension, specimens notched to various depths and angles. Because of the uncertainties in Kuntze's (and McAdam's) analysis of the stresses (which have been pointed out by Sachs16) and the inherent nonuniformity in the stress distribution in notched bars, the results of such investigations are difficult to interpret. A more direct method of measuring the effect of deformation on the fracture stress was suggested in previous papers"-18 and has been utilized in the present investigation. The present paper concerns itself primarily with the behavior of notched impact specimens. The effects of strain rate, temperature, and stress distribution, which are discussed with reference to the impact specimen, apply just as well to the behavior of metal at the bases of notches in any engineering structure. All that is necessary is to determine the stress distribution in the structure at the base of the notches.

Jan 1, 1944

By John H. Hollomon

The interpretation of notched-bar impact results has been a matter of controversy since the introduction of more or less standard tests by Fremont,' Charpy2 and others at the turn of the century. Many investigators3-l1 have contributed to the understanding of the significance of such tests. Several symposiums12,13 have been held with the express purpose of discussing the significance and interpretation of the impact tests. It is not the purpose of this paper to review all these contributions to the development of the knowledge on this subject, but rather to present an interpretation of notched-bar impact tests that appears to be in agreement with the available published data. Fundamentally, the interpretation discussed in this paper of the brittle failure of some steels in notched-bar impact test is similar to the qualitative analysis presented by Ludwik3 in the I92o's. Essentially, Ludwik stated that the function of the notch was to increase the tensile stress necessary for yielding, and that brittle failure occurred when the stress necessary for yielding exceeded the normal stress required for fracture (with no plastic deformation). Ludwik, however, had no means of measuring this normal stress necessary for failure of a plastically* undeformed metal, therefore he could not extend his interpretation beyond the qualitative stage. Kuntze14 and recently Mc-Adam15 attempted to determine the effect of deformation on the stress necessary for fracture by testing, in tension, specimens notched to various depths and angles. Because of the uncertainties in Kuntze's (and McAdam's) analysis of the stresses (which have been pointed out by Sachs16) and the inherent nonuniformity in the stress distribution in notched bars, the results of such investigations are difficult to interpret. A more direct method of measuring the effect of deformation on the fracture stress was suggested in previous papers"-18 and has been utilized in the present investigation. The present paper concerns itself primarily with the behavior of notched impact specimens. The effects of strain rate, temperature, and stress distribution, which are discussed with reference to the impact specimen, apply just as well to the behavior of metal at the bases of notches in any engineering structure. All that is necessary is to determine the stress distribution in the structure at the base of the notches.

Jan 1, 1944

By R. W. Ph. D. Raymond

PROFESSOR W. P. BLAKE, in a note to his Catalogue of California Minerals, pointed out that the mining districts of the Pacific slope are arranged in parallel zones, following the prevailing direction of the mountain ranges. This interesting generalization has been more fully illustrated and connected with the geological history of the country by Mr. Clarence King, who sums tip the observed phenomena as follows: "The Pacific coast ranges upon the west carry quicksilver, tin, and chromic iron. The next belt is that of the Sierra Nevada and Oregon Cascades, which, upon their west slope, bear two zones, a foot-hill chain of copper mines, and a middle line of gold deposits. These gold veins and the resultant placer mines extend far into Alaska, characterized by the occurrence of gold in quartz, by a small amount of that metal which is entangled in iron sulphurets, and by occupying splits in the upturned metamorphic strata of the Jurassic age. Lying to the east of this zone, along the east base of the Sierras, and stretching southward into Mexico, is a chain of silver mines, containing comparatively little base metal, and frequently included in volcanic rocks. Through Middle Mexico, Arizona, Middle Nevada, and Central Idaho is another line of silver mines, mineralized with complicated association of the base metals, and more often occurring in older rocks. Through New Mexico, Utah, and Western Montana lies another zone of argentiferous galena lodes. To the east, again, the New Mexico, Colorado, Wyoming, and Montana gold belt is an extremely well-defined and continuous chain of deposits." These seven longitudinal zones or chains of mineral deposits must

Jan 1, 1873

By L. L. Wyman

Previous studies1 by the writer dealing with the embrittlement of copper have been concerned with the behavior of various pure and deoxidized coppers when exposed to an oxidation-reduction cycle, and the consequent evaluation of these materials on the basis of their resistance to this action. No attention was devoted to the variations in penetration of embrittlement with time, when these copper materials are exposed to a strong reducing gas, such as hydrogen, nor to the variations in oxygen penetration, with time and temperature, into the "pure" coppers. The cause of the embrittlement is the reduction of the oxygen in the copper by the hot reducing gas, so that a consideration of time, temperature, the occurrence of hydrogen and oxygen must be given. For the purpose of differentiating some of the involved factors, the present work may be divided into two separate series of experiments. The first of these deals with the oxidation of purified coppers under various conditions and then the subjection of these to a standard hydrogen treatment. The second series concerns the reduction, under different conditions, of tough-pitch coppers of several oxygen contents. The resulting data will give the rates of oxidation, and of reduction, for the materials involved. The first series of experiments will reveal how rapidly copper may become oxidized, while the second series will indicate how rapidly embrittlement will penetrate into an oxygen-containing copper when it is exposed to hydrogen at different temperatures. Materials For the purpose of determining these variables, three types of material were selected, to cover the extremes in the ranges of materials commercially obtainable. The first class of materials is represented by an oxygen-free copper, as well as the high-purity vacuum-melted copper2 used in previous work. These materials were selected to determine the variation of oxidation with time and temperature, by oxidizing these coppers under various combinations of these factors, and noting the effect as indicated by a

Jan 1, 1934

By E. A. Barnard

ARSENIC is a very old substance. The ancients speak of it in their writings, and its use has developed very little until recent years. The ancients used it in making pigments, in medicine, and for poison. They also tell of the difficulties of handling it-an experience which is very similar to our own. Until about 10 years ago, arsenic was very cheap and was a drug on the market. About that time the boll weevil began making serious inroads on the American cotton crops, and after much investigation the Depart-ment of Agriculture developed a very successful poison for this pest, consisting of calcium arsenate. The weevil pest has continued, and as the cotton planters have become convinced that calcium arsenate is the best material to use against the weevil, the demands for it have been steadily increasing, resulting not only in a rising price of arsenic but in a very serious shortage so far as our country is concerned. So serious has this shortage become, and so vital is it to the cotton growing industry, that Congress has appointed a committee to investigate and report on the situation. A meeting of arsenic producers and consumers was held in New York last December to take stock of the situation and to see what could be done. The extreme increase in, the market price of arsenic-from 6 c. to 15 c. per lb. in less than a year-has been very harmful to the producers as well as to the consumers. Some very interesting' data were brought out at this meeting, as follows: CONSUMPTION PER YEAR, SHORT TONS Arsenate of lead 2,000 Paris green 1,200 Proprietary mixtures 750 Sheep dips : 1,000 Weed killers 1,500 Glass : 2,000 8,450 1922 Consumption as calcium arsenate 4,000 12,450 1923 Estimated consumption as calcium arsenate... 12,000 Estimated 1923 consumption 20,450

Jan 8, 1923

By Plato Malozemoff, A. M. Gaudin

IN modern practice the major portion of an ore is reduced to flotation size by fine grinding. As the result of grinding fine enough to liberate most of the minerals, a substantial portion (generally 5 to 15 per cent) of the ore is inadvertently reduced to a size much finer than that necessary for liberation. This portion of most flotation pulps is very refractory to recovery by flotation. A reduction of one-quarter or more in recovery in this range of extremely fine particles can be observed. The loss in metals caused by overgrinding is appreciable. That this loss is characteristic of very fine particles has been suspected for some time;(l)† however, it was definitely quantified only recently.(2) Definite reduction in float-ability with reduction in particle size beyond a critical size of maximum floatability can be accepted now as an established fact. Formulating the Hypothesis In looking for the cause of the ill behavior of the finest particles it may be well to consider the essential differences between fine and coarse particles. A difference that immediately comes to mind is their intrinsic difference in size and consequently in relative extent of surface. If one agrees that attachment of mineral particles to bubbles must follow direct encounter of particles with bubbles one is forced to conclude(3) that the probability of encounter between a mineral particle and a bubble varies directly as the size of the particle, provided the particle is small compared to the bubble. In other words, the finer the particle the poorer its chance of being recovered in a given time of flotation. There is an effect, implicit in this theory, which should overcome the effect of excessive fineness of the particles; namely, flocculation of the particles. The floccules can be conceived as being simply larger particles and therefore capable of becoming attached to bubbles. And, indeed, in all the cases in which a sulfide mineral of near-colloidal size was successfully floated the mineral (but not necessarily the gangue) was flocculated. Moreover, it was shown experimentally(4) that galena previously flocculated by inorganic flocculators and then added to gangue

Jan 1, 1935

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.' However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By R. Woodward Moore

A graphical method of analyzing the data obtained from shallow earth-resistivity depth tests is presented. The method is based upon empirical results and has no theoretical basis. The usual apparent resistivity-electrode spacing curve is used together with a cumulative resistivity-electrode spacing curve plotted on the same sheet. The greatly reduced scale required for plotting the cumulative values of resistivity together with the effect of the summation of the individual resistivity values serves to minimize the effect of purely local surface anomalies and inadvertent errors of measurement. The point of intersection of tangents or straight lines drawn to intersect at zones of maximum curvature in the cumulative curve indicates the depth to the underlying material. Numerous figures are presented in which data from published reports and from recent field studies are analyzed and the results compared with actual depths established by borings or with depth values obtained by the use of theoretical methods of analysis. Smoothly rounded curves of apparent resistivity such as are often obtained in the field, and which have been a serious drawback to attempts to analyze the data empirically heretofore, appear to be susceptible to rather accurate analysis by the method described. The method is best suited to analyses involving shallow two-layer formations. It has been applied successfully, however, in analyzing the data obtained from tests made over shallow three-layer formations. As with most empirical methods, its chief advantage is its simplicity and ease of application. There have been published many papers that discuss the interpretation of data obtained from earth-resistivity tests when using the four-terminal method of electrode spacing developed by Wenner.' The majority of these have dealt with theoretical analyses for two-layer and three-layer formations. Some sets of "master curves" have been presented for use in analyzing field data to determine the depth to the first and possibly the second horizon below the earth's surface. Although practically all of these theoretical methods of analysis have appeared to have particular merit and some have been used successfully in practice, they have been found to be of little value where the local conditions surrounding the test failed to conform to those assumed in the theory. In certain fields, particularly in civil engineering, relatively shallow explorations are often involved and geophysical methods of test must compete with the direct methods of exploration ordinarily used. Only when it can be demonstrated that geophysical methods of test can materially reduce the time and cost of a given exploration project will the civil engineer abandon direct methods in favor of the interpretations of geophysical exploration data. Empirical methods of analyzing earth-resistivity data have been used in many instances in the past. Such methods have been employed for a number of years by the Public Roads Administration in research work relative to the application of

Jan 1, 1946