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By R. W. Fountain, M. Korchynsky

The precipitation phenomena occurring in cobalt-tantalum alloys have been investigated in the temperature range frm 500" to 1050°C by correlating the results of metallographic, X-ray, micro-and macrohardness, and electrical resistivity studies. The property andmacrohardness,changes were found to depend on 1) general precipitation, and 2) lamellar precipitation. Two new intermetallic phases have been identified: 1) a Co3Ta, a metastable ordered face-centered-cubic compound, and 2) a stable ß Co3Ta phase of hexagonal structure. In addition, the previously reported Co2Ta phase was found to exist in two allotropic modifications: the hexagonal MgZn,-type and the cubic MgCu2-type Laves phases. SINCE a large variety of structures can result as a consequence of the decomposition of a solid solution, predictions on the nature of property changes are difficult, if not impossible, to make. For any rational attempt to correlate properties and structures of a precipitation-hardenable alloy, a detailed understanding of the kinetics of decomposition and morphology of phase separation, as well as knowledge of phase relationships, appears to be prerequisite. Information of this type has been accumulated in the past for many alloy systems, both of theoretical and pastforpractical importance.1,2 Although the presence of intermetallic compounds has been reported in cobalt-base alloys,3 the amount of published information on precipitation-hardenable cobalt-base systems is very limited. A survey of the binary phase diagrams of cobalt indicates that cobalt-tantalum alloys might be of interest as typical of other cobalt-base systems in which Laves phases of the A,B type can be precipitated from solid solution. The present work has been undertaken, therefore, to study the kinetics and morphology of the precipitation reaction in this system and to establish a base for a correlation between the structural aspects and properties in this class of alloys. PREVIOUS WORK The only available phase diagram of the cobalt-tantalum system is based on the work of Koster and Mulfinger. According to these authors, the maximum solubility of tantalum in cobalt is about 13 pct (at 1275°C) and. less than 7 pct at room temperature. Tantalum additions lower the temperature of allotropic transformation of cobalt (about 420°C), and at 7 pct Ta, the high-temperature face-centered-cubic modification (ß cobalt) is retained at room temperature. The precipitating phase was originally designated as Co5Ta2 compound (55.2 pct Ta, about 1550°C melting point), but subsequent investigations by wallbaum5" identified this constituent as the A,B-type Laves phase. Wallbaum's data indicate that there are two modifications of this intermetallic compound: one richer in cobalt (Co2.2 Tao.8)of the hexagonal MgNi, type; and another of a higher tantalum content (Co2Ta) of the cubic MgCu, type. On the other hand, Elliott7 found that the cobalt-rich alloy (CO2.10,Tao.~l) was predominantly the cubic MgCu, type at 800°C and a mixture of both the MgCu2 and the hexagonal MgZn,-type Laves phases at 1000°C. At 1200°C, Elliott found only the MgZn, type while at 1400°C, he observed only the MgCu2 type. At the stoichiometric composition, Co2Ta, Elliott reported only the cubic MgCu2-type Laves phase in the temperature range of 600oto 1600°C. The precipitation of the cobalt-tantalum intermetallic compound is accompanied by a marked increase in hardness. According to Koster's4 data, the Brinell hardness of an 8 pct Ta-Co alloy increases from 230 to 340 upon short-time aging at 800°C. EXPERIMENTAL PROCEDURE The binary cobalt-tantalum alloys investigated contained 5, 10, and 15 pct Ta. The range of tantalum additions was thus slightly broader than the reported minimum and maximum solid solubility limits of tantalum in cobalt (7 and 13 pct, respectively)4 The alloys were vacuum-induction melted in a magnesia crucible using cobalt rondelles and technically pure tantalum sheet as raw materials. Deoxidation of the melt was accomplished with carbon, and the chemical analysis of the alloys is given in Table I. The effect of isothermal aging treatments on the progress of precipitation was studied on samples cut from cast ingots. These samples were solution treated for 2 hr at 1250°C and water-quenched. Aging was conducted in the temperature range from 500" to 1050°C for periods between 15 min and 1000 hr and followed by water-quenching. To prevent contamination from the atmosphere, all samples were sealed in evacuated Vycor or quartz tubes for heat-treatments. For solution treatment, argon at 0.2 atmospheric pressure was introduced prior to sealing of the capsule to prevent collapse at high temperature, and titanium sponge was placed at one end of the capsule to act as a getter. MACROHARDNESS The effect of aging on Vickers hardness (Dph) of

Jan 1, 1960

By J. Chipman, T. P. Floridis

The equilibrium of gaseous H2O-H2, mixtures with liquid iron is used to establish the activity coefficient of dissolved oxygen as log f o = — 0.20 [%O]. Discrepancies in earlier work are explained or eliminated. Additions of cobalt, molybdenum, tungsten, and platinum increase the activity coefficient of oxygen whereas copper and gold decrease it. THE importance of dissolved oxygen as a refining agent in liquid steel has led to a number of studies of its thermodynamic properties. It is the purpose of this paper to examine the effects of a number of alloying elements on the activity of oxygen in the steel bath. As a preliminary to the study of the effects of alloying elements, it seemed desirable to examine certain minor discrepancies in the published data on the properties of oxygen in simple iron-oxygen solutions. The activity and free energy of oxygen in liquid iron were studied by chipman1 in 1933 by means of the reaction h2(g)+-o = H2O (g);K; = PH2O/PH2[% O] [1] The data were in fairly good agreement with calculations from results on the similar reaction CO (g) + O- = CO2 (g); K2 =P CO2/P CO [% O] [2] which had been obtained by Vacher and Hamilton2 as an incidental part of their study of the reaction of carbon with oxygen dissolved in the melt. It was found that the equilibrium ratio k1 was not a true constant but varied with the oxygen concentration in the manner shown in Fig. 1, which is copied from the original paper. This early observation has been refuted in subsequent work but is confirmed in the present paper, and an explanation of the discrepancy can now be presented. In Fig. 1, the two points on the extreme right were disregarded in drawing the

Jan 1, 1959

By Cyril Stanley Smith

IsolatEd alloys of copper and silicon were prepared and examined by chemical methods more than one hundred years ago, but it was not until the work of Rudolfi l that the equilibrium relations were studied. The early history of the alloys was well described by Baradue-Muller 2 and need not be further discussed here. The diagram of Rudolfi, based entirely on thermal observations, showed sillcon to be soluble in copper up to 4.5 per cent. at 849" C., at which temperature there was a peritectic horizontal resulting from the formation of a ß phase with about 7.4 per cent. silicon from a and liquid with 7.85 per cent. silicon. The ß phase was believed to form a eutectic with Cu3Si at 820" C. and 9.8 per

Jan 1, 1929

By Cyril Stanley Smith

IsolatEd alloys of copper and silicon were prepared and examined by chemical methods more than one hundred years ago, but it was not until the work of Rudolfi l that the equilibrium relations were studied. The early history of the alloys was well described by Baradue-Muller 2 and need not be further discussed here. The diagram of Rudolfi, based entirely on thermal observations, showed sillcon to be soluble in copper up to 4.5 per cent. at 849" C., at which temperature there was a peritectic horizontal resulting from the formation of a ß phase with about 7.4 per cent. silicon from a and liquid with 7.85 per cent. silicon. The ß phase was believed to form a eutectic with Cu3Si at 820" C. and 9.8 per

Jan 1, 1929

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By A. Raman

The Nb-Co system was nuestigated in the range 10 to SO at. pct Co with X-rays. A pt phase with the W6Fe.r-type structure occurs in the system between 46 and 52 at, pct Co. Its unit-cell dimensions are nearly identical to those of the p Phases found in the Nb-Fe and Nb-Ni systems. Two Laves phases, one having the MgZnz-type structure and the other the MgCuz-type structure, already t-eported in the literature, are found to exist in the system. The ,l.IgZnz-type phase occurs between 62 and 64 at. pct Co. A MgNi2-type Laves phase, reported in the literature, is no! obtained. A binalry phase is found to exist belozv I000C around 82 at. pct Co. THE cobalt-rich side of the system Nb-Co has been repeatedly investigated by previous inestiators" and the following intermediate phases are known to occur: NbCo, which crystallizes in the MgCu2-type structure and Nbc03,' reported originally by Wall-bam, which has the MgNiz-type structre. Jordan and uwez' as well as lliott' were unable to find the MgNiz-type phase. Two phases, designated as x and y, were reported by Saito and eck.' The phase x was inferred to have a narrow composition range near 77 at. pct Co. No published work is known to the author which reports the investigations in the niobium-rich portions of the system. This paper presents the results of an investigation in the Nb-Co system between 10 and 80 at. pct Co. EXPERIMENTAL PROCEDURE Two or three grams of the alloys under investigation were prepared using niobium (99.9 pct +) and cobalt (98.8 pct + with 0.14 pct Fe and and 0.03 pct C) in a tungsten-electrode arc furnace under commercial argon atmosphere. They were then wrapped in molybdenum sheets and annealed for a period between 5 days and 1 week at 1300°C in high vacuum (10-" orr) or in evacuated quartz amules for 2 weeks at 1000°C. Powders of -325 mesh size were prepared for X-ray work by crushing and grinding the specimens. Subsequent reannealing of the powders was not undertaken since most of the alloys were brittle and broke easily. X-ray powder patterns of the as-cast and annealed samples were prepared in a Siemens cylindrical camera (57.3 mm radius) with Cr-K, radiation. A Siemens diffrac to meter was used to get the X-ray patterns of some new phases. Metal log raphic examination of the alloys supplemented the X-ray findings. RESULTS The results of the X-ray and microstructural analysis Of the alloys are in in Table I. The lattice parameters of the phases are listed in Table 11 for quick reference. A set of micro photographs in Fig. l(n) to (j) show the microstructures of some alloys. A probable equilibrium diagram is drawn in Fig. 2

Jan 1, 1967

By William H. Emmons

Discussion of the paper of William H. Emmons, presented at the Canal Zone meeting, November, 1910, and printed in Bulletin No. 46, October, 1910, pp. 767 to S37. CHARLES R,. KEYES, Des Moines, Ia. (communication to the Secretary*) :-It is not in a spirit of criticism that I offer a supplemental suggestion or two on the subjects covered by this valuable and highly instructive memoir. There are two points which, in my opinion, should have received greater emphasis in Mr. Emmons's excellent paper. One is the fundamental role played by the chlorides under certain conditions in ore-formation. The other is the possible establishment of geographic relationships among the four phenomena of (1) excessive chloridic content of mine-waters; (2) the abundance of chloridic compounds of the precious metals ; (3) the presence of. manganese oxides; and (4) the diminishing importance, in ore-genesis, of the metallic sulphates. Although Mr. Emmons's notes refer to gold alone, it may be pertinently asked whether the same principles do not hold good for silver and copper also, since these metals form, together with gold, a distinct and well-known chemical group. That the reactions involved apply equally well to the other two metals mentioned, is shown by a number of recent observations and discussions. Chloridic ores of silver are, as I have lately endeavored to show, mainly worked in. arid or desert regions only ; and the great deposits of disseminated copper-ores are similarly characteristic of such regions, in which both classes doubtless owe their formation to the abundance of saline materials derived from desert dusts, and to the .plentiful and almost universal presence of manganese oxide. Under these climatic conditions, silver is somewhat more abundantly deposited than copper and gold, because its chloride is so much * Received Nov. 11, 1910.

Jun 1, 1911

By J. David Lowell

For his contributions to the field of mining geology, a striking example being his brilliant inte.rpretation of the complex geologic history of the San Manuel District (Pinal County, Arizona) which resulted in the discovery of the Kalamazoo orebody, and for his lecture, "Copper Resources in 1970." On a low desert ridge six miles south of Cairo lie the remains of the world's earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radiocarbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy. Evolution of the Copper Industry The copper ore mined by the ancients was high grade, and the copper produced was expensive. The copper industry began with narrow high-grade veins, but has evolved to the point where massive earth-moving equipment can be operated in huge, low-grade open pits. Indian pits dug before 3000 B.C. in the Lake Superior district were in ore which averaged 15% Cu. His- torical research done by Arthur Brant has shown that copper cost in the Middle East in 1840 B.C. in terms of 1970 labor dollars was about $25 per lb. The copper mined in northern Europe in 1540 in the time of Georgius Agricola averaged about 8% Cu, and the cost in 1970 labor dollars was about $10 per lb. Average ore grade had dropped to about 6% Cu in 1890, and the cost of copper in the U.S. in 1970 dollars was about 45¢ per lb. Butte, Mont., was a good example of the efficiently operated vein mines of this time. In 1906, Daniel Jackling made a dramatic entrance into the copper scene with the Bingham Canyon open-pit copper mine and proved that more profit was possible mining 2% porphyry copper ore on a

Jan 1, 1971

By AIME AIME

IV. THE BOUNDARY BETWEEN STEEL AND IRON. It would be well to decide on a definite carbon-content to serve as a boundary line between ingot-iron and ingot-steel, between puddled-iron and puddled-steel, and between any other varieties of wrought-iron and weld-steel. Two plans have been considered. One is to draw this line at 0.32 per cent. of carbon or its equivalent in other elements, for the reason that this carbon-content appears to correspond to the critical point, 0, in the diagrams of Roberts-Austen and Rooze-boom.8 This has the merit of corresponding to a definite physical boundary. The other plan is to draw the boundary at 0.20 per cent. of carbon, because this is a convenient place to separate the important classes " soft steel " and " half-hard steel," so that if this point was adopted "ingot-iron " would be synonymous with "soft steel," and " ingot-steel " would be the equivalent of the two classes, " half-hard steel " and " hard steel."

Mar 1, 1908

By J. S. Vanick

An extremely hard, tough, and strong, white or chilled cast iron has been applied for the past several years to industrial and mining services in which its unusual properties have been confirmed by its ability to deliver in many instances much better performance than plain chilled iron, or other wear-resistant materials. It is being produced regularly by alloying a good base composition of chilled or white cast iron with essentially 4 to 6 per cent of nickel and 1 to 2.5 per cent of chromium. Such a material can attain a hardness exceeding 600 to 750 Brinell as against 380 to 530 for corresponding grades of plain chilled iron. The strength is approximately doubled and the toughness significantly increased. These properties make it especially useful for many applications requiring a high hardness for resistance to wear, abrasion, attrition, deformation; to some extent to high compressive loading and to a lesser but important degree to corrosive action. A wide variety of commercial castings is being successfully produced from this iron, ranging in size from the small grain-grinding plates or burrs through medium-sized castings such as sand pumps up to large, heavy castings such as rolls for metal rolling or cement grinding. The composition of this white cast iron may be roughly bracketed within the range shown in Table 1.

Jan 1, 1933

By J. A. Berge, R. S. Mateer, R. G. Aspden

IN a study of the cold-rolling characteristics of iron-base alloys with 3 to 12 pct Al, the influence of aluminum content on the cold-rolling textures was evaluated. This work was undertaken to determine if binary iron-aluminum alloys possessed cold-rolling textures similar to other body-centered-cubic alloys and to contribute additional information on the effect of solute concentration on the cold- rolling textures. Gradual changes in cold-rolling textures with an increase in solute content have been observed in copper1 and in titanium.2 Iron-base alloys containing 3.0, '6.0, and 12.0 pct aluminum were vacuum-induction-melted in a magnesia crucible and permanent-mold cast. The materials used were high-purity electrolytic iron and 99.99 pct grade aluminum. Each ingot was 1 in. square in cross section by 12 in. in height. The bottom half of each ingot was soaked for 1 hr at 1000°C and rolled at 1000°C to a thickness of 0.055 in. with the long axis of the ingot parallel to the rolling direction. The strip was reheated between passes to maintain a rolling temperature of 1000°C.

Jan 1, 1960

By John Alden

A CONSIDERABLE PROPORTION of the tonnage of aluminum used today has at some stage during its manufacture, been rolled. I. For one, therefore, was particularly pleased to hear that this Society was to hold a symposium on rolling of nonferrous metals. Metallurgists can well afford to direct their close attention to the metallurgy involved in this important operation. To one who has seen today's high production rolling mills for aluminum it is difficult to realize that the first aluminum rolling mill For sheet was installed a scant 55 yr ago, in 1892. This mill was a three-stand train of 2-high mills, driven by a steam engine and was operated for many years successfully rolling aluminum sheet. Mills for the rolling of aluminum rod were installed in 1899 to meet the demand For manufacture of electrical conductor wires and cables. Bars and rods in straight lengths were also made. While these mills were the first built for rolling aluminum products of these types some rod had previously been rolled on brass and copper mills. Not until many years later, in 1929, however, Were facilities provided for the rolling of structural shapes, such as I-beams and channels. Growth of the aluminum sheet business and the necessity for economical manufacture soon brought the realization of the economies resulting From-the rolling of sheet in long lengths and coiling it. A five-stand continuous mill driven by a steam engine, was in operation late in 1907. This took aluminum slabs coating from

Jan 1, 1948

By F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck's work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck's outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."' We were not however very successful in getting values for Schenck's "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck's work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952

Note by the Secretary.-—In the preceding communication of Mr. Rickard, in the present discussion, as printed in Trans., xxiii., the loss of quicksilver at Pestarena, reported on p. 569, as 230 and 234 grammes per metric ton, is stated as equivalent to about 74 pounds per short ton avoirdupois—an obvious error, which escaped correction in my reading of the proofs, and was not discovered until after Vol. XXIII. had left the press. The true equivalent is 0.46 pound or about 7 1/2 ounces (instead of pounds) per short ton.— R. w. R. Philip Argall, Denver, Colo. (communication to the Secretary) : Mr. Rickard's last contribution to this discussion* calls for some reply from me, if only by way of defending myself against the charge (p. 569) that my criticisms of his paper were "unnecessarily hypercritical and occasionally unfair." At the same time I am fully aware that our Transactions are not the place for mere personal controversy, and that the sole object of discussion is to define differences of opinion, and defend opposing views as a means of eliciting the truth. Mr. Rickard disclaims the statement, which he says I attributed to him, that in the slow-crushing Gilpin county mills the pyrites remain longer in the mortar than the other portions of the ore. My understanding of his statement was based on the following passages in his paper: " Particles of ore, which have heen pulverized to a fineness which would permit of their exit through the screen, are enabled to settle towards the bottom of the mortar. It would he expected that the heavy metallic minerals occurring in the ore would, because of their greater specific gravity, be most affected by this feature of the treatment. In practice this is found to be so. The fine slimes contain a large proportion of metallic sulphides, generally valuable on account of their close association with the precious metals, while the coarsest particles to be found in the tailings usually consist of quartz and other minerals forming the less heavy gangue (Trans., xxiii., 139).

Jan 1, 1895

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper' the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called ('deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,' it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2'3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,' indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By W. van der Knapp

A theoretical and experimental ana1ysis is given of the change in volume of a porous medium due to changes in external and internal pressures. The result enable one to deduce directly the effect of large increlents in stresses. It is shown that the three-dimensional representation of the volume of a nonlinear porous system is a cylindrical rules surface, the generating lines of Which have a slope according to the solid rock compressibility. Analytical expression for such a ,surface is very simple. It follows that the bulk and pore compressihilities depend only on the difference between pore fluid and external hydrostatic pressure, i.e., the effective rock frame pressure. From measurements on a number of sandstones as well as limestones it can be conduded that for practical values of this effective frame pressure the pore compressibility falls in the range between the compressibility of water and that of undersaturated crude oil. In general, pore compressibility is found to be higher the lower the porosity. For a particular limestone reservoir pore compressibility and porosity could he related by means of a simple empirical formula. Results from the described study find a direct applicxtion in material balance calculations and in prob1ems of liquid flow through porous media. Since the elastic constants of the rock bulk material enter into equatiorls for velocity of acoustic waves, the results are also of importance for calculating rates of wave propagation in these media. It is shown for sandstones with 1.5 to -10 prr cent porosity that laboratory measured porosities may differ from those lender reservoir conditions by about I per cent of their value. The difference for low porosity limestotnes can be of the order of 10 per cent. The subsidence caused by elastic deformation of reservoir rock is shown to he very small. General formulas relating pore and bulk volume to external and internal pressure can be derived, as has been shown by Biot1, Gassmann2 and Geertsma.2 Their theories describe the differential change in volume caused by a variation in pore fluid tension and external hydrostatic tension. It has been known for a long timei that the stress-strain relations of a packing of spheres are essentially noninear. Our experiments show that for almost all reservoir rocks which arc elastically deformable the relation between volume and loading is also a nonlinear one, resembling that of a packing of spheres very closely. The behavior of these media is often described by using the linear stress-strain relations for small incremental stresses and strains in the vicinity of a pre-stressed condition." The present study differs from these considerations in that it enables one to deduce the effect of large increments in the stresses directly. In analogy to the stress tensor for a homogeneous body the stress tensor for a porous body can be written in the conventional way: where the tensor components, o, and t, represent the total forces acting on the faces of a unit cube of porous material. This tensor can be split into two parts. a hydrostatic and a deviatoric part, as follows2,3,1 where the component of the hydrostatic stress system, a. equals The hydrostatic stress causes a change in volume whereas the deviatoric stress system gives rise to a change in shape only. One of the difficulties in describing changes of volume occurring in reservoir rocks is that the relations connecting these volume changes with external and internal stresses are essentially non-linear. A complete description requires the bulk volume, V,,, as well as the pore volume,V,,. to be known as a function of both the changes in pore fluid tension (v) and the hydrostatic tension on the outer boundary.

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1'700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By George Young

DURING the spring of 1910 I visited a number of open-pit brown-coal mines and underground workings in the vicinity of Halle, Halberstadt, Leipsic, Cologne and Bonn. The notes which I took and the observations which I made at the time have been condensed and make up the principal part of this paper. Certain supplementary information has been taken from several sources which are given in the paper. The mining of brown coal is one of the important industries of Germany. The coal varies in color from dark brown to almost black and is soft like loam. Pieces of wood and strips of bark and, even parts of tree trunks are frequently encountered in the excavation although the coal for the most part consists of a pulverulent, more or less matted mass of small particles of vegetal matter. It is a product between peat and lignitic coal. An analysis, taken from Coal Resources of the World shows the approximate composition of the material: Moisture, 53.73 per cent.; ash, 4.98; fixed carbon, 18.08; volatile carbon, 23.31 per cent. The principal characteristic is the amount of moisture. This seldom runs less than 48 per cent. The ash is usually low and ranges from 5 to 10 per cent. The sulphur content is usually less than 0.5 per cent. The heating effect of the fuel ranges from 2,000 to 2,500 calories.

Jan 2, 1916

Jan 1, 1970

By G. Townsend Harley

STOPING methods in which shoveling plays an important part are gradually being replaced by other and cheaper methods. But there will always be considerable shoveling done underground in stopes as well as in drifts, tunnels, urinzes, and shafts. At the mines of the PhelpsDodge Corporation at Tyrone, N. M., the cost of shoveling in all stopes in 1917 amounted to 24c. per T. In the top-slice stopes for the same period, it cost 27 c. per T. or 16 per cent, of the total cost of these stopes. The tonnage for shovelers from all stoping was 9.3 T. per man, and for topslicing 8.2 T. per man. These stopes were not unduly hot, and there was not more than the usual amount of timber to interfere with the work of the men. The tonnages obtained per shoveler were considered low; first, because of a poor grade of Mexican labor, many of the men having come in from railroad grading camps; and second, because of a poor spacing of raises, especially in the top-slice stopes, where, in general, they were spaced 25 ft. by 66 ft. (7.6 by 20.1 m.) centers. The average wage per laborer shift was $2.67 during the year. It was thought, however, that even under these conditions the men were not producing the tonnage that they should, so, with the consent of the management, the writer undertook to determine how the general efficiency of the underground shoveling could be improved. No predetermined plan for conducting these experiments was arranged because we had no definite ideas as to the scope of the work or the number of elements into which the investigation would resolve itself, before all of its phases could be determined. We were sure, however, that any work that would thoroughly cover the ground would have to be in the nature of a systematic time study, combined with a course of instruction in correct shoveling methods and adequate and intelligent supervision of the work. Two or three companies in the Southwest have done some work to determine the proper shovel to be used undcrground, but so far as is known the work has been limited to equipping certain parts of their mines with a particular type and size of shovel and thereafter watching the cost and efficiency records. In each case it seems to have been the shovel that held the 21-lb. (9.5-kg.) load that gave the bcst results. Excepting personal communications from these companies, the only data available on scientific shoveling are contained in F. W. Taylor's book, "The Principles of Scientific Management," and D. J. Haucr's article, in The Contractor for March 29, 1918, "A Hundred Hints for Shovelers." This paper discusses and draws conclusions from several thousand time-study readings, taken both on the surface and in the mines for nearly a year. A sufficient number of readings were taken on each factor in the problem for the plotting of curves of the performances and to obtain accurate indices of the work to be expected from this class of labor. The work is not as complete in all of its details as we would like to havc it, because we were forced to stop the work temporarily, owing to the numbcr of men going into the National service and our inability to get others who could make time studies. The results obtained so far, however, have been of such a startling nature that we have decided to submit them at this time, subject to future modification. It is hoped, also, that a free discussion of this paper will lead to a disclosure of any errors that may have becn embodied and offer some valuable suggestions for the conduct of future work.

Jan 1, 1920