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By L. G. Austin, R. R. Klimpel

This article demonstrates that the Gilvarry and Klimpel-Austin equations for the random fracture of solids are incorrect by deriving intuitively correct expressions for simple cases and showing that the foregoing equations do not reduce to right answers. It is the purpose of this article to point out serious errors in some existing treatments of the random fracture of solids. Gilvarry ' gives the equation where B(y,x) is the cumulative fraction by weight of particles which fall below size y when particles of size x are broken. The constants i, j, k contain shape factors and densities of flaws leading to propagating fracture surfaces. The authors believe this equation to be incorrect. Klimpel and usttin' give where r~ is the number of fracture planes originating from edge flaws (per L where L is the edge length of the original particle), rs is the number of fracture planes originating from flaws on the particle surface (per S where S is the surface of the original particle) and rv is the number of fracture planes originating from flaws within the particle volume. This equation is also incorrect. The failures of these equations will be demonstrated by deriving intuitively correct expressions for simple cases and showing that the Eqs. 1 and 2 do not reduce to the correct answer. In this process, the flaws in statistical reasoning inherent in the derivations of Eqs. 1 and 2 become apparent. THE KLIMPEL-AUSTIN EQUATION Eq. 2 was derived by considering a set number of fracture planes occurring spatially at random within a given particle. This case will be treated here in its simplest form: a line with 1, 2, 3, etc., fractures occurring at random. This is illustrated in Fig. 1, with the original length of the line as Vo. The breakage of a long, thin, brittle fiber is a corresponding physical case, with the volume of a fragment proportional to its length. Assuming independence of the occurrence of the fractures, the probability of any one fracture occurring in length dV is dV/V0. The probability of the first fracture occurring at a length V to V + dV is dV/Vo. For the case of only one fracture per particle, formation of a number-size distribution of the left-

Jan 1, 1969

By T. R. Graham, R. S. Dean. J. R. Long

Following the development of electrolytic manganese production by the Bureau of Mines, an extensive program was planned to study the character of this high-purity product and its possible utilization in various alloy combinations. Previous work reported in the literature concerning alloys containing substantial amounts of manganese dealt largely with material prepared from relatively impure grades of the metal, and in many instances the impurities thus introduced did not permit true evaluation of manganese as an alloying element. One phase of the Bureau's program included a general review of the system and the establishment of the physical properties of copper-manganese-zinc alloys, using electrolytic manganese, and with particular emphasis directed to compositions within the alpha solid solution area. A number of reports of the work on alloys in this system, giving specific data concerning the equilibrium system and some of its alloys, have already been published. One study' established the alpha solid solution area at various temperature levels and composition ranges up to 50 pct manganese. Other investigation reports presented the properties of selected alloys; namely, a 65 pct copper, I0 pct manganese, 25 pct zinc alloys;1 a sensibly white manganese brass composed of 70 pct copper, 20 pct manganese, 10 pct zinc,3 and a series of alloys with a constant copper content of 60 pct and 5 to 25 pct manganese, balance zinc.4 In these reports tensile properties as influenced by cold-working and subsequent annealing were given in detail. Additional data are now available on other alloys of the alpha region up to 50 pct manganese, and these, together with previously published information, are sufficiently complete to establish the relationship between properties and composition for this portion of the ternary system. The present report is a summary of the tensile properties of wrought alloys in the form of sheet and rod stock. The summary is necessarily limited to data for only one condition of cold-work and a single annealing temperature, since a complete exposition of all the data available would be too extensive for this presentation. Nevertheless, it is possible to make a reasonable approximation of the tensile properties in other conditions of cold-worki"g and annealing by a correlation of the data previously presented on specific alloys and the data given here.

Jan 1, 1947

By R. S. Dean. J. R. Long, T. R. Graham

Following the development of electrolytic manganese production by the Bureau of Mines, an extensive program was planned to study the character of this high-purity product and its possible utilization in various alloy combinations. Previous work reported in the literature concerning alloys containing substantial amounts of manganese dealt largely with material prepared from relatively impure grades of the metal, and in many instances the impurities thus introduced did not permit true evaluation of manganese as an alloying element. One phase of the Bureau's program included a general review of the system and the establishment of the physical properties of copper-manganese-zinc alloys, using electrolytic manganese, and with particular emphasis directed to compositions within the alpha solid solution area. A number of reports of the work on alloys in this system, giving specific data concerning the equilibrium system and some of its alloys, have already been published. One study' established the alpha solid solution area at various temperature levels and composition ranges up to 50 pct manganese. Other investigation reports presented the properties of selected alloys; namely, a 65 pct copper, I0 pct manganese, 25 pct zinc alloys;1 a sensibly white manganese brass composed of 70 pct copper, 20 pct manganese, 10 pct zinc,3 and a series of alloys with a constant copper content of 60 pct and 5 to 25 pct manganese, balance zinc.4 In these reports tensile properties as influenced by cold-working and subsequent annealing were given in detail. Additional data are now available on other alloys of the alpha region up to 50 pct manganese, and these, together with previously published information, are sufficiently complete to establish the relationship between properties and composition for this portion of the ternary system. The present report is a summary of the tensile properties of wrought alloys in the form of sheet and rod stock. The summary is necessarily limited to data for only one condition of cold-work and a single annealing temperature, since a complete exposition of all the data available would be too extensive for this presentation. Nevertheless, it is possible to make a reasonable approximation of the tensile properties in other conditions of cold-worki"g and annealing by a correlation of the data previously presented on specific alloys and the data given here.

Jan 1, 1947

By J. R. Long, E. L. Anderson, R. S. Dean, F. S. Wartman

TITANIUM has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, 'methods required for its fabrication, and the properties that may be produced in this interesting metal. METHODS OF PREPARING METALLIC TITANIUM Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,2 van Arkel,3 and Fast,4 subsequently confirmed the facts that pure titanium is a ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent 'solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agents2 with sufficient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By J. Gurland

The strength variation ofWC-Co alloys with composition and particle spacing falls into two ranges. 1) Above a critical value of the mean free path, the strength follows a dispersion hardening relation; it is proportional to the volume fraction of WC and in-versely proportional to the particle size. 2) Below a critical value of the mean free path, the strength variation is based upon the Griffith criterion of fracture and is controlled by the case of crack propagation. The maximum strength is attained when the structure and load just satisfy the critical conditions for spontaneous crack propagation. THE relation between the strength and the structure of cemented carbides is of interest not only for its own sake but also for its contribution to the understanding of composite materials in general. The cemented carbides are essentially aggregates of a brittle carbide constituent and a ductile binder phase and, at certain structures of intermediate composition, the composite alloys attain strengths far higher than those of the separate constituents in bulk. It is this variation of strength with structure which will be discussed. The experimental procedures of sample preparation, mechanical testing, and quantitative metallo-graphic analysis have been described in Ref. 1. The reported strengths are the maximum fiber-stresses in bending calculated on the basis of completely elastic behavior. The plastic contribution to the over-all deformation is small and was neglected in the calculations (the elongation at fracture of the most ductile alloy, 50 pct WC-50 pct Co, is less than 0.5 pct).2 The pertinent structural parameters are: f, the volume fraction of tungsten carbide; p, the mean free path through the binder phase; the contiguity C, defined as the average fraction of surface area shared by a particle of wc with all neighboring particles of the same phase; and d, the average equivalent spherical diameter of the WC particles. The strength variation of WC-Co alloys with composition and particle spacing is shown in Fig. 1 and Table I, which are based partly on previously published data' and partly on new experimental work which extends the range to higher values of the mean free path. Each data point represents the average of five samples. For a given composition, the transverse rupture strength reaches a maximum

Jan 1, 1963

By John Campbell

An approximate theoretical model is proposed to quantitatively predict freezing ranges Tf and hydrostatic tensions P developed within solidifying binary alloys, allowing for a certain amount of diffusion of solute in the solid during solidification. The maxima in ATf and AP as functions of composition are shorn to occur at smaller solute concentrations than would be expected from the equilibrium diagram, and are found to correspond closely to experimentally observed maxima in microporosity. THE freezing range of simple binary alloys appears to have been little studied, except for certain indirect observations on the defects, particularly microporosity and hot tearing, arising in long freezing range materials. Two theories relating to the freezing range of alloys and its effect upon porosity are reasonably well established, and appear to have been held in isolation from each other: a) From purely equilibrium considerations early researchers expected that an increase in solute content of an alloy should increase the freezing range (defined here as the equilibrium freezing range ?Tf = Tl-Ts where TL and Ts are the liquidus and solidus temperatures, respectively) and thereby increase the width of the pasty zone for a given set of conditions. This in turn should increase the difficulty of feeding the residual liquid through the dendrite mesh to compensate for the contraction on solidification, and consequently tend to increase the observed amount of porosity. From qualitative observations on steels Czikel1 reports an increase in porosity with increasing carbon content up to 0.46 pct C. More careful measurements by Whittenberger and Rhines2 on fourteen different alloy systems showed an approximately linear relation between ?Tf and pct porosity (although unfortunately the precise experimental data is not given). b) Conversely however, other authors3"5 propose that porosity is reduced by the presence of increased amounts of eutectic present at the final solidification temperature. Lees7 and Bochvar6 claim that the hot tearing of alloys is similarly reduced. Scheuer8 has put forward a theory to explain this effect, Fig. 1. The argument is basically that solidification progresses on a plane front through a relatively open dendrite network and is thus (the argument is not developed more explicitly) easier to feed. One would expect effect a) to operate at low solute contents, and b) to be important at higher solute contents, so that at some critical composition a max-

Jan 1, 1970

By C. A. Wert, M. G. Coleman

The Zener relaxation in alloys in the a! solid-solution region of the Cu-Ni-Zn ternary system has bear investigated. Of the binary solid solutions that bound this region, Cu-Zn and Ni-Zn exhibit measurable Zener peaks whereas Cu-Ni does not. At constant atomic percent copper, the Peak height drops uni.forinly from the value in the Cu-ZTL binary to zero in CIA-Ali. The cariation of peak ternperatuve with composition is linear. At constant atomic percent zinc, the peak height in the ternary alloys goes through a large maximum as compared with the binary values. The temperature of these peaks varies smoothly with composition. The half-width of the peaks in the ter nary alloys, however, are much larger than those in the binaries. A large enhancement of the relaxation strength of the Zener relaxation in ternary Au-Ag-Zn alloys as compared to the relaxation strengths in Au-Zn and Ag-Zn binary alloys was observed by Firson and ert.' Since this effect was unexpected, the present study was devised to investigate whether enhancement of the Zener relaxation in ternary alloys is a general feature or is particular to the Au-Ag-Zn system. We have chosen the Cu-Ni-Zn alloy system for this investigation. Measurable Zener relaxations are observed in both the Cu-Zn and the Ni-Zn binary systems, but not in the Cu-Ni binary system. A large solid-solution region extends to large concentrations of zinc, making it possible to vary composition of the alloys over a wide range without crossing phase boundaries. EXPERIMENTAL PROCEDURE Two series of alloys were prepared. the first at constant atomic percent copper, the second at constant atomic percent zinc. The compositions of these alloys are shown by the circles in Fig. 1. The alloys were prepared by melting the individual components, each of which had previously been vacuum-melted, in an evacuated quartz capsule in an induction furnace at 1500 C. The capsules containing the molten alloys were quenched in water to reduce coring. Any individual melt which exceeded 0.001 pct weight loss was discarded. The ingots were swaged to a 50 pct reduction of area and annealed for 1 week in an evacuated quartz capsule to aid homogenization. The alloys were then

Jan 1, 1967

By E. C. Truesdale, W. K. Waring

The Research,Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kids of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein' some years ago: ZnO + CO = Zn + CO2 [i] C + COj = 2CO [2] Each of these reactions is dependent upon the other for the supply of CO and COz, respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + He = Zn + HZO 13] C + Hz0 = CO + He U3 While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse Ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction is still the faster. He also says (p. 48), "At temperatures . . . be- -tween 1100' and 1300°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates.'' In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of ' a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented.*

Jan 1, 1944

By A. M. Gaudin

The flotation process has been applied extensively in the mineral and chemical fields. This paper reveals results obtained by an exploration of an application to the biological field. In many ways this study was indeed an exploration since so many factors are different. In the mineral field, the particles, both those floated and those not floated, cover a wide range of sizes and shapes; in the biological field, the particles of one population are primarily of one or two sizes and one or two shapes. This identity in size and in shape gives biological systems the advantage of homogeneity. In the mineral field the particles may be as coarse as a millimeter; in the biological field the size may be a micron, or less. In the mineral field the particles may have a gravity several times that of water so that their apparent gravity is quite substantial. Microorganisms, on the other hand, may have a gravity so near that of the liquor that their settling velocity in the liquor is vanishingly small. These two facts conspire to make bubble-particle encounter in the pulp-body less likely. Finally, microorganisms are living, reproducing, and dying-all of which does not help the experimenter get a balance of materials. The analytical problems, too, are extraordinarily difficult, for the organisms can contain only elements that occur in their environment, although at a different level of concentration. The chemical composition of the surface of microorganisms is readily altered. In spite of these areas of difficulty, microorganisms can be floated to leave practically water-clear tailing, they can be floated from each other and, in fact, the same organism can be fractionated into a float that differs from the sink. SIZES AND SHAPES OF ORGANISMS Most ore pulps are described with reference to the percentage of the pulp that is fine enough to pass a 200-mesh sieve. Thus a copper-ore pulp may be 80% -200 mesh. Since 200 mesh equals 74 µ, a 2000-mesh particle would be 7.4 µ in diameter, and a 20,000-mesh particle would be 0.74 µ. The microorganisms with which this work is concerned are of the order of magnitude of 20,000 mesh. We have worked with Escherichia coli, the colon bacillus, Bacillus cereus, Bacillus subtilis, Bacillus megaterium, and Serratia marcescens. In some pioneer work, Dognonl,2 reported the use

Jan 1, 1962

By Daniel D. Pollock

The il'lott and Jones theory of thermoelectricity predicts that the absolute thermoelectric power of alloys of transition and noble metals should be a maximum when the concentration of the noble metal is approximately 55 to 60 at. pct. An examination of the emf of a series of relatively pure alloys of copper and nickel shows that the predicted maximum occurs at about 57 at. pct Cu. This excellent agreement with the theory is considered to substantiate the Mott and Jones theory of thermoelectricity for binary alloys of transition elements. This theory is extended to show that the emf behavior of dilute, ternary copper-nickel base alloys, which contain approsimately 60 pct Cu and 40 pct Ni, may be described in terms of a scattering mechanism. The scattering effect of a third element is demonstrated to be a function of its valence and its period in the periodic table. Small amounts of solute elements have additive scattering effects upon the emf of the Cu-Ni base. The Mott and Jones equation is modified to include this scattering parameter. This adaptation accurately describes the thermoelectric behavior of ternary and quaternary CLL-Ni base alloys. An empirical form of the modified Mott and Jones equation is derived which permits the calculation of thermoelectric power with an average error of less than 0.4 pct at 500 "C. CONSTANTAN has long been used as a thermocouple element. Its approximate composition varies from 50 pct Cu, 50 pct Ni to 65 pct Cu, 35 pct Ni. Small amounts of manganese, iron, and other elements have been used to modify the composition in order that the resultant emf vs platinum conforms to nationally accepted table. Adjustments of this type are made on a purely empirical basis. Constantan was originally made in Germany and was imported into this country for thermoelectric and electrical resistance purposes. During World War I, the supply of this material became seriously depleted. The work of Bash4 was done in this period in order to develop a satisfactory substitute for the imported material. Bash's empirical work on Cu-Ni alloys is still the basis for all commercial constantans made in this country. No reexamination of the electrical properties of this system has been made, despite the fact that it is now well known that Bash's alloys contained impurities which strongly affected their thermoelectric behavior.

Jan 1, 1962

By R. V. Norris, E. W. Parker

Edward W. Parker,* Philadelphia, Pa.—At the New York meeting of the Institute a year ago, Mr. R. V. Norris presented a paper on anthracite mining costs, in which he gave the results of an intensive study of this subject by the Engineers' Committee of the United States Fuel Administration. Within the last 30 days, the Federal Trade Commission has issued an official report on the same subject, which covers a longer period of time and comprises statistics of realization values and margins that were pot comprehended in the paper by Mr. Norris. As, however, the data utilized by Mr. Norris formed also a part of the basis for the report of the Federal Trade Commission, a brief digest of the latter may not be out of place at this meeting. The report of the Federal Trade Commission covers primarily the two calendar years 1917 and 1918, divided into five periods which furnish opportunity for the study of how the influence of certain definite factors affected either the cost of production or the price, or both, during the 24 months. The first period, January to April, 1917, which may be considered the basic period, comprised the 4 months in 1917 during which the wage agreement of May, 1916, without modification, was in effect. During this period, the labor cost on fresh-mined coal is placed by the Commission's report at $1.79 per gross ton, the total cost at $2.66, the average realization at $3.29, and the "margin" (sales realization over total f.o.b. mine cost) at $0.63. The second period covers the four months from May 1 to August 31, during which time the first of the supplemental wage agreements (supplemental to the agreement of 1916) was in effect. It was also the period during which the summer discounts were in effect and when prices were practically fixed by a voluntary agreement between the operators and the Federal Trade Commission. It was, further, the period in which the 75 cents differential on prepared sizes permitted to the individual operators by the Federal Trade Commission began; at that time, also, on account of war conditions an unusually large quantity of steam sizes were marketed at exceptionally good prices. On account of the two latter conditions, not explained in the Commission's report, the "margin"1 on operating

Jan 1, 1920

By A. W. Schillinger

Drilling was not entirely satisfactory in the search for native copper in the Osceola amygdaloid footwall, for oreshoots mined were more continuous than drilling indicated. The Geophysics Dept of Michigan Technological University developed a portable induced polarization drill hole probe with a 3-electrode configuration and a sampling radius of 5 ft ±. A 20 ma current of alternately reversed polarity is pulsed at 3.5 sec intervals and readings are taken every 2 ft. Potential is read during the "on" cycle for resistivity determinations. During the "off" cycle, after 10 ms delay, the 1P potential is sampled for 10 ms and recorded. Resistivity (ohm-ft) and "S" values (mv/v) are plotted on semi-log paper. A lithologic log is plotted based on resistivity and anomalous S values noted. The low resistivity amygdaloid contains sills of high resistivity basalt. Verified by core logs, contacts between amygdaloid and basalt could be picked to ± 0.5 ft from resistivity alone. Lithologic logs of long-steel holes, based on resistivity, then replaced sludge logging. An S value of 30 mv/v was established as the lower limit of diagnostic 1P effects in mineralized amygdaloid and 50 mv/v as a threshold value for ore. Of 914 footwall zones drilled, 315 were probed yielding 203 anomalies. Success increased from 34% for drilling to 72% for drilling and probing. As checked by mining, 46 probe results were 78% correct. Failures were due to the instrument not detecting copper or to the misinterpretation of an anomaly. No false anomalies were found. During the past ten years, the Calumet Div. of Calumet &Hecla, Inc has conducted extensive exploration and mining in the footwall of the Osceola amygdaloid lode in the native copper district in Michigan's Upper Peninsula. In an attempt to delineate more clearly the extent and nature of high-grade footwall copper mineralization, 876 diamond drill and long steel holes aggregating slightly more than 47,000 ft have thus far been drilled from the accessible hanging-wall workings in the Osceola No. 6, 13, 14 and 15 shafts. Early in this program it became obvious, through inspection of footwall workings in progress, that due to the erratic and bunchy occurrence of the native copper in the footwall zone, the exploration drilling was failing to outline completely the extent of the oreshoots. Early drilling re-

Jan 1, 1964

By S. M. Parmley

Experience has shown that there are some factors connected with the drying of fine washed coal that are not present in drying of slack coal as normally practiced at cement kilns or pulverized coal plants. It is the purpose of this paper to show some of these variations as they have been encountered under actual operation. The Champion No. 1 cleaning plant of the Pittsburgh Coal Co. uses the wet system of cleaning coal. The plant is equipped to produce commercial sizes or mixtures, the primary sizes being plus 6 in. and 4 by 6 in., which are hand-picked. Minus 4-in. sizes are all cleaned by the wet process. To produce a commercial product as free of moisture as possible, the washed coal is first passed over sizing and dewatering screens, then each size except the — ?-in. coal is conveyed to loading booms by slow-moving draining conveyors. As the +?-in. sizes are not heat-dried, no data will be given, as it is the purpose of this paper to describe the heat drying of — ?-in. coal as practiced at the Champion No. 1 plant of the Pittsburgh Coal Company. To fully appreciate the conditions, it must be remembered that the — ?-in. product is now shipped at a lower moisture content than when received from the mine. The incoming coal in the — ?-in. size will average 5 per cent. moisture and the shipped product 3 per cent. moisture. This is a case where a wet process gives a reduction of both ash and moisture in the fine sizes. The shipped product, therefore, is more uniform in all characteristics, and uniformity of product is the most important single factor in coal preparation. The 0 by ?-in. coal is first dewatered on slow-moving continuous bucket dewatering elevators, running at the rate of 40 ft. per minute, with 48-in. perforated buckets with ¼ by 1½-in. slots, spaced ? by 2?-in. centers staggered. The moisture in the coal discharged from the elevators runs 20 to 28 per cent., depending on the fineness of the product. The discharge from the dewatering elevator is further drained on a drag-type conveyor equipped with ½-mm. wedge wire screen. The conveyor discharges coal with an 18 to 25 per cent. moisture to three centrifugal dryers of the Carpenter type. The Carpenter dryers

Jan 1, 1931

By M. H. Richman, L. M. Markowitz

MUCH of the available information on which the heat treatments of a particular steel are based is found in the isothermal-transformation diagram. Such is the case despite the fact that the usual thermal treatments involve continuous transformations, i.e., transformations which occur on cooling, rather than isothermal transformations. This rather unusual practice is continued because of the abundance of published isothermal-transformation diagrams1, 2 which are relatively easy to determine experimentally as compared to continuous-transformation diagrams.3, 4 However, this can easily lead to the production of improper micro-structures and may not allow full advantage to be taken of the inherent hardenability of a steel. A mathematical method of estimating the continuous-transformation diagram from the available isothermal data was developed by Grange and Kiefer;5 but, due to the mathematical approximations required in the calculations, the computation of continuous-transformation diagrams has been limited to individual cases and no large-scale compilation of these diagrams is available. With the present availability of high-speed digital computers, the problem of time-consuming approximations may be minimized and continuous-transformation diagrams may be constructed with the insertion of isothermal data into a basic program. It is the purpose of this report to announce the availability of such a program and compare the computed and experimental continuous-transformation diagrams for two different steels. Let us first review the method of Grange and Kiefer5 and then compare the results of the machine calculations with the experimentally determined diagrams. In order to apply this method, one requires the isothermal-transformation diagram and a set of curves representing cooling at constant rates. A section of an isothermal-transformation diagram is shown in Fig. 1 together with a cooling curve of M0F per sec. The cooling curve is constructed to start from the A1 (eutectoid) temperature if the transformation product is the eutectoid microconstituent (i.e., pearlite or bainite), from the A3 temperature if the product is primary ferrite, or from the 4, if it is proeutec-toid cementite. The cooling curve in Fig. 1 intersects the curve representing the start of isothermal transformation at a point A' corresponding to a temperature TX and a time fX. An arbitrary lower temperature To (on the

Jan 1, 1968

By Shueling Woo, Charles S. Barrett, Robert F. Mehl

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By V. Patarini, D. Kuehl, F. Galasso, M. Salkind

In recent years, a great deal of research has been directed toward the production of continuous low-density, high-strength, high-modulus boron fibers for aerospace applications. A technique which has proven to be quite successful for forming these fibers involves the reaction of boron trichloride and hydrogen on a hot tungsten wire. In this process, a boron fiber is produced which consists of a tungsten boride core covered with amorphous or crystalline boron depending on the temperature of the preparation.2,3 The purpose of this paper is to present the properties which have been obtained to date from measurements and observations on these fibers. Selected samples of boron filament produced by reacting boron trichloride and hydrogen on a 0.5 by 10-3 in. diam tungsten wire substrate using different reacting temperatures were cross-sectioned, polished, and photomicrographed with cross-polarized light. The temperature of the wire was measured using a two-color optical pyrometer. Photomicrographs of these samples are shown in Fig. 1. Three general types of boron, in addition to the tungsten borides, have been identified by means of X-ray powder diffraction techniques: a) at low temperatures (below 1400°C) the boron is deposited in the amorphous form; b) at temperatures between 1400° and 1500°C the boron is deposited in the ß tetragonal form; and, c) above 1500°C the boron is deposited in the B rhom-bohedral form. In the depositing range of 1400" to 1500°C the boron initially deposits as amorphous and becomes crystalline as evidenced by the large equi-axed grains which then merge into columnar grains in later stages of boron deposition. This can be seen in Fig. 1 and has been observed in the X-ray patterns of these fibers, which contain both halos from the amorphous boron and lines from the ß tetragonal form. Above 1500°C the only boron reflections observed in the X-ray patterns were those of the ß rhombohedral form and only columnar grains are seen in the photomicrographs. Photomicrographs of the surface in Fig. 2 show the smooth-surface kernal-type deposition which corresponds to the amorphous form and the rougher surfaces which correspond to the crystalline form. Mechanical measurements were made on amorphous boron produced at 1300°C rather than the crystalline boron because the strengths of these filaments were greater and were more consistent. A tensile tester consisting of a fixed crosshead containing a double

Jan 1, 1967

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION of iron in austenite is a process which may play a significant role in some of the practically important reactions which occur in solid irons and steels. It also provides a system in which the interaction of vacancies on substitutional sites and atoms in interstitial positions may be investigated. For both purposes, accurate values of the diffusivities are required. Two sets of previous measurements exist, each containing features which require checking. In the course of an investigation to determine the rate of diffusion of iron in certain steels, Garwick and Rosenqvist' measured the self-diffusion coefficient of iron in a 0.10 pct* C steel and obtained a dicated that while at lower temperatures D increased with increasing carbon content, at the higher temperatures it first increased and then decreased. At the same time the activation energy decreased linearly from a value of 69,000 cal per g-atom for pure iron to 33,000 cal per g-atom at 1.06 pct C. This rapid decrease in activation energy implies that iron at higher temperatures within the austenite range would diffuse more slowly in high carbon steels than in steels of lower carbon content. Experimental Procedure The radioactive iron used in this work was obtained from Oak Ridge National Laboratory. The unit consisted of about 1 microcurie each of Fe7 and Fe It was allowed to decay for two years. At the end of this time most of the Fe with a half-life of 46.3 days, had decayed, while most of the original Fe(half-life 2.91 years) still remained. The iron as chloride was extracted into an ether layer, using the method of Ashley and M~rray. After evaporation of the ether the iron chloride was dissolved in 250 ml of aqueous solution containing 2.4 gpl Fe. The compositions of the steels used are listed in Table I. Disks of ¾ in. diam and about ¼ in. thick were machined from these steels for use in diffusion couples. The disks were surface ground on both sides to ensure parallel opposite faces. One face of each disk was polished through 000 emery paper. Half of the prepared disks were plated with radioactive iron. For this, 1 ml of the radioactive iron

Jan 1, 1957

By J. B. Wagner, B. Swaroop

The atomic ratios of oxygen to iron in zlarious corn-posilions of wustite in the vicinity oj the reported p to n transformation were determined in the temperalure range between 950" and 1250°C. For these conditions, equilibrium vacancy concenrations have also been determined at vatious mixtures of C0,-CO. The data show a continuos introduction of iron vacancies as oxygen is introduced into wuistite. No phase change is observed with in the wuustite field. However, the value of n in the isothermal oxygen pressure dependence, the weight change shifts to 1ower values as the concentration of oxygen increases. WUSTITE is a metal deficit semiconductor with the majority lattice disorder being cation vacancies. Using the notation similar to that of Kroger and ink,' the dissolution of oxygen into wiistite using C02-CO mixtures is represented by, WHere v+! denotes a cation vacancy with k effective negative charges and kh • denotes k electron holes, h -. Applying the law of mass action and assuming a dilute solution of defects in the wiistite yields Where the square brackets denote concentrations. Furthermore, when k = 2 the cation vacancies are completely ionized, and both the concentration of cation vacancies and the concentration of electron holes are proportional to the third root of the ratio, PC /PCo. This analysis is valid for one particular mael based on an ideal solution at elevated temperatures (in this case t > 1000°C). At lower temperatures, it has been shown2 that the pressure dependence of the electronic conductivity changes in a manner which suggests that vacancies interact with or "trap" electron holes. At the very high concentrations of defects, 10'' to 10" per cu cm, these simple models no longer hold. Recently Tannhauser,3 Geiger et a1.' Bransky and Tannhauser; and Hillegas' have found an apparent p to n transformation in wiistite in the temperature range of 950" to 1300°C. This junction was found by thermoelectric and electronic conductivity measurements. Geiger eta1.' found that the electronic conductivity became almost independent of the oxygen pressure at high temperatures and oxygen concentrations within the experimental error. In addition, Vallet, Raccah, and coworkers6'7 have reported the existence of several "varieties" of wiistite which were reported to exist within what was heretofor presumed to be a

Jan 1, 1968

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

WHEN one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed' that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others.2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between , phase layers formed by diffusion, in the Cu-Zn system, § and furnishes further evidence in support of the principle. MATERIALS AND METHODS The Cu-Zn system is especially suitable for these studies since the high vapor pressure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals-and with various loads, then the plates were annealed for .4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold worked layers from the finished crystals

Jan 1, 1944