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By B. N. Das, J. B. Darby, P. A. Beck, Y. Shimomura

A POWDER pattern for the (Cr, Mo, Co)R-phase annealed at 1200°C was reported in 1951.1 Through the courtesy of Prof. D. P. Shoemaker of Massachusetts Institute of Technology the authors became aware of inconsistencies of this pattern with that to be expected from the structure of the R-phase, as determined by Komura, Shoemaker, and Shoemaker.' In addition, Professor Shoemaker also noted that the powder pattern reported8 for the (Cr, Mo, Co)D-phase, annealed at 1300°C, agreed fairly well with that to be expected from the newly determined structure of the R-phase. In view of these findings, the previously reported powder patterns of the R-phase and of the D-phase were compared carefully. It was found that most lines in the two patterns (22 lines) were to a fair degree of accuracy related to each other by a single conversion ratio for the corresponding d spacings. The value of the conversion ratio was found to be 1.0058, so that the d spacings of the D-phase pattern previously reported were larger than the correspond- ing d spacings for the reported R-phase pattern by approximately that factor. The intensity relationships between corresponding lines in the two patterns were similar, as judged visually. The following exceptions were noted: Lines Nos. 2, 3, 19, 20, 21, 22, 23, 24 and 25 of the D-phase pattern,:' all designated weak or very weak, were missing in the apparently somewhat fainter R-phase pattern used.' Lines 1, 2, 3, 5, 15 and 34 (all weak or very weak), reported for the R-phase, were missing in the D-phase pattern, Table I. In view of these observations it seemed probable that the two patterns differed from each other mainly by a slight change in lattice parameters (with c/a remaining approximately constant), and that the pattern previously reported for the R-phase contained some weak extraneous lines, most likely to be attributed to impurities. In order to check the foregoing assumption, two specimens of an alloy containing 43 pct by weight of cobalt, 41 pct molybdenum, and 16 pct chromium, which was within the composition range of stability of both the D-phase at 1300°C and of the R-phase at 1200°C, were homogenized at 1200 and 1300°C, respectively, and quenched. X-ray diffraction patterns of the powders of these two specimens, obtained with CrK radiation, were compared carefully with each other and with the D-phase pattern previously

Jan 1, 1959

Executive HOWARD N. EAVENSON, Chairman FREDERICK M. BECKET EDGAR RICKARD ERLE V. DAVELER WILLIAM WRAITH Finance HENRY KRUMB, Chairman PAUL I). MERICA J. V. W. REYNDERS H. G. MOULTON, Consultant Admissions JOHN M. LOVEJOY, Chairman GEORGE D. BARRON DONALD M. LIDDELL ELI T. CONNER WILLIAM W. LYNCH Alternates WM. H. BASSETT, JR. L. B. LINDEMUTH W. A. SINSHEIMER

Jan 1, 1934

By A. G. McGregor

In the Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 1/2 in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining CO.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally 1/4in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft, from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 1/4-in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar —water, sodium silicate, and finely ground silica—was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By Walter Stern

THE self-potential or spontaneous polarization method is one of the oldest in the field of electrical exploration. When applied in prospecting for ore bodies, it is one of the most rapid and inexpensive means of locating indications of ore bodies at shallow depth. Usually, the procedure is to survey the equipotential lines of the electrical field that is generated by the electrochemical activity of the ore near the ground-water level, and to localize the so-called negative centers or points of greatest negative anomaly. Another field procedure involves the measurement of potential differences along potential profiles, generally laid out at right angles to the assumed strike. Again, in such survey, the basis for establishing the presence of ore is the location of negative potential anomalies. The earlier writers on the subject, notably Schlumberger1 and R. G. Wells,2 did much to clarify the fundamental electrochemical phenomena involved. Interpretation of the field data, however, remained largely qualitative. In 1925, A. Petrovsky3 analyzed the relation between the shape of the potential anomaly curve and size and depth of an ore body by assuming the subsurface body to be a polarized sphere.4 Along similar lines of approach, Edge and Laby5 considered the ore body a dipping sheet with limited extent in the direction of strike, while Poldini6 based the theory on the assumption of a dipping bar. The following study endeavors to enlarge [ ] FIG. I.-ORE BODY CONSIDERED AS DIPOLE upon these earlier investigations and attempts, on the basis of the potential distribution of a polarized bar, to indicate certain characteristics of the anomaly curve that make possible the determination of depth, size and dip of a subsurface body. THE SPONTANEOUS POLARIZATION FIELD SET UP BY AN ORE BODY If a sulphide ore body is subjected to oxidation varying in degree in its upper and lower parts according to the difference in the concentration of oxygen within the surrounding medium, an electrical potential field is set up. The form and distribution of this field will be investigated herein with special reference to its components on the earth's surface. Under the simplifying assumption that the ore body may be considered as a dipole with the point sources QI and Q2 situated at its upper and lower ends (Fig. I), the potential of the spontaneous polarization at point P is given by the following equation:

Jan 1, 1944

One-half fare return rate again available to members of the Institute and dependent members of their families. DON'T FORGET YOUR RAILROAD CERTIFICATE Over 300 members of the A. I. M. E. and dependent mem-bers of their families attending the last annual meeting se-cured return railroad tickets at half price by means of the railroad certificate, thereby saving several thousand dollars. DIRECTIONS 1. Be sure to obtain your railroad certificate when pur-chasing your railroad tickets for the meeting or you will lose money. 2. Purchase your tickets at regular one-way adult tariff fare between the dates specified for your territory in the accom-panying table. 3. Present your certificate for valida-tion at Institute headquarters in New York immediately after registration. Certificates will be validated on Feb. 21 and 22 between 9 a. m. and 5.30 p. in. 4. You must use your return half-rate tickets not later than Feb. 27. 5. Use the same route for both going and return trip. PLEASE REMEMBER THIS 1. Unless-250 certificates are validated at headquarters it will be impossible for anyone to secure the reduced rate. 2. Unless you secure a certificate you cannot take advantage. of the half-rate return fare, even if the necessary 250 certificates are validated.

Jan 2, 1928

By A. A. Collins

H. R. BIANCO*—I should like to ask Mr. Collins if that statement he made about the addition of drosses to the blast furnace slowing down the blast furnace is a result of his own experience or a result of the experience of some older metallurgists; and perhaps I should ask him to define the type of drosses that he means. A. A. COLLINS (author's reply)— That has been my own personal experience with dross. On various occasions at Chihuahua we attempted to incorporate the dross in our regular blast furnace charge and to shut down the dross re-verberatory to try to save some money. As expected, we had very poor results. I think that Ed Fleming will well remember on one occasion, that was back about 1933, when we attempted the first experiment along this line, and as a result of the sulphur addition to the blast furnace to matte out the copper we ended up with hanging furnaces and mushy slags and abandoned the dross experiment, once again turning to the use of the reverbera-tory for handling dross. H. R. BIANCO—Is that dross you refer to from the drossing kettle ? A. A. COLLINS—Yes, the dross that I am referring to came from drossing kettles. Furthermore, to back up my previous assertion, I had occasion in 1943, while up at Leadville, to once again experience the routing of dross through the blast furnace with its sulphur addition, since they had no dross re-verberatory, and to observe that once thf dross was removed, the furnace was speeded up almost 100 tons a day. All of these are personal experiences and I think that Mr. Feddersen also has had a little experience along this line —in fact, I believe all of us have had some experience. H. R. BIANCO—I know at Trail they recirculate considerable dross through the blast furnaces and we also recirculate dross at Herculaneuin and I am not aware that it has done much towards slowing down the blast furnace. A. A. COLLINS—We have always had very poor results. In the first place you have got to add a sulphur addition to pick up that copper and once you do that, that sulphur is apt to combine with some of the zinc and you are going to form a little mush; before you know it you have furnace hangs and a poor working furnace. Now of course that depends on the amount of zinc you have on charge. But in 1943, Leadville had roughly about 7 pet zinc in their slag and it worked very poorly. Previously when they had 4 or 5 pet zinc in their slag it did not matter. B. L. SACKETT* At Tooele we had a great deal of experience with copper. We have always been able to keep a lead well, however, in spite of the fact we have run as much as 5 pet copper and only 15 pet lead on the charge. But regarding the handling of dross, our dross reverberatory furnace is only 7 or 8 years old. Before that we recirculated the dross through the furnace and thought we were doing a pretty nice job. Of course these things are all more or less relative—in other words you establish a certain condition much better than one of a few years ago and possibly as good as any other of which you know and you think you have pretty good results. When we first took the dross off of the blast furnace and put it through the dross reverberatory furnace we immediately found out that we had gained something very real in furnace speed. Since that time there have been occasions when, because of the dross reverberatory being down, we have had to use dross again through the blast furnace and that has checked our original experience in slowing down the furnace very definitely. So we feel that a dross reverberatory is a very valuable asset at the Tooele Plant. A. A. CENTER*—Mr. Sackett's being here reminds me of trying to run with a minimum of lead concentrates the maximum of dross producing electrolytic zinc plant residue. He came up from International Smelting Co. to help us get started on that. We took an old copper blast furnace at Great Falls, Montana, and made a lead furnace out of it by putting a lead well on the other long side which of course is a very unorthodox lead blast furnace. Our aim was to treat the residue from the electrolytic zinc plant, as I said, with a minimum of lead concentrates. That meant a maximum amount of dross. At that time selective flotation was not general practice, so our zinc concentrates ran relatively high in copper and other dross-producing elements; and of course these were largely in the zinc plant residue. I think we might call it muscle metallurgy, but we had an interesting, successful experience there and we ran for over a year thanks to Mr. Sackett's helping us get started. I have the details, but time does not permit. We did well enough so that the A. S. and R. Co. at East Helena kept boosting up the offer to us for the electrolytic zinc plant residue and there was not enough lead concentrate to supply two lead smelters there in Montana, so the matter finally finished up by the A. S. and R. Co. taking all of the residue under long term contracts.

Jan 1, 1950

By R. W. Guard

ALTHOUGH etching techniques have been developed for revealing dislocation sites in several metals and ionic crystals,h t is valuable to extend the technique to new metals. An etch pit method for nickel has been developed on the basis some suggestions of Dr. John R. Cuthill of the National Bureau of Standards who had observed etch pits in creep specimens of nickel. The etchant used was proposed first by wensch2 for revealing grain size in nickel. The present paper describes the evidence that the technique can be used to reveal dislocations and gives the conditions under which etching can be carried out. The specimens examined were vacuum melted high-purity Ni (99.985 pct Ni) and commercial "A" nickel (99.8 pct Ni). Both materials contained greater than 0.008 pet C and had been annealed in nitrogen or dry hydrogen at 1100o to 1200°C. This gave a grain size of 1.5 mm in the high-purity nickel and 0.050 mm in "A" nickel. Tensile specimens (0.254 in. diam) were deformed from 0.25 to 10 pct at room temperature and then heated for 1/2 hr at different temperatures from 400" to 900°C. The specimens were sectioned longitudinally then polished electrolytically in 60 pct H2SO4 and etched in 35 pct H3PO4 solution at 0.2 to 0.4 v for 30 sec to 3 min. The best method for setting the proper voltage for etching is to increase the voltage until gas bubbles are evolved vigorously from the specimen and then cut it back by 10 pct. It is necessary to heat the specimen above 500°C after deformation in order that etch pits will be formed. This "decoration" treatment permits carbon to segregate to the dislocation rendering them sensitive to etching. It was demonstrated that carbon was the decorating impurity by decarburizing some specimens in wet H2 at 1200°C. The susceptibility to etch pitting was lost following this treatment but could be restored by carburizing in contact with graphite. Some rearrangement of the dislocations in the as-deformed structure occurs on heating at 500oC and above so that the technique can not be used to study the nature of dislocation patterns in deformed specimens. Extended etching does not change the number of pits although the background becomes rough and the pits quite large. The polycrystalline specimens with various strains were examined after annealing at different temperatures. Typical patterns are shown in Figs. 1 and 2. In the unstrained specimen, Fig. 1, the density of pits is 2.5 X 10' per sq cm. All grains show pits regardless of their orientation although there is a

Jan 1, 1961

By W. N. Carr, J. R. Biard, B. S. Reed

An analysis of the semiconductor injection laser is presented which is based on a phenomenological model using device and material parameters. The intent of the laser threshold analysis is not to predict from theory the actual threshold current density but rather to provide a logical means of interpreting experimental results. The device and material parameters have been selected such that they describe both the threshold conditions and quantum efficiency of the lasev. A technique is proposed whereby the current required to obtain a population inversion is predicted from device 1-V characteristics. Experimental data are presented which support the analysis. THIS investigation is concerned with the characteristics of GaAs lasers fabricated in this laboratory. However, the assumptions used in these calculations should not limit their application to GaAs alone. It is felt that the analysis is sufficiently general to be useful in describing the operation of other semiconductor-laser materials. ANALYSIS heavily doped semiconductors to be considered. The absorption and/or generation of optical radiation may be completely specified in terms of q(E) and the probability functions f,,(E) and f,(E) which define the occupancy of the valence-band and conduction-band levels, respectively. The symbols used in this analysis are listed at the end. Following the approach of all' it can be shown that the effective gain coefficient, g, in the plane of a forward-biased P -N junction is g(E)=-ai@)[1-fv(E)-fc(E)] [1I In particular Eq. [I] holds for the photon energy at which lasing occurs, Ep. Throughout the following discussion Eq. [I] is considered only for the lasing transition E = Ep. For simplicity the functional energy dependence of the various factors is omitted in subsequent equations. Unless otherwise stated the symbols used represent the values at Ep. If the analysis is limited to the P-type side of the laser junction, the function q(l -f,,) is recognized as the band-to-band absorption in the P-type material at thermal equilibrium. Under forward-bias conditions the function f, is determined by the electron quasi Fermi level in P-type material. For sufficiently large forward bias the second term in Eq. [3] will become dominant and net gain will result; i.e., g will become positive. In order to simplify the subsequent analysis several assumptions are in order at this point. a) No conductivity modulation occurs. /„ is independent of f, and therefore go is a constant. b) The P-type material is heavily doped such that the degeneracy of the valence band permits popu-

Jan 1, 1964

By RICHARD L. HUMPHREY

IT IS proper that there should be a brief accounting of the stewardship which was entrusted to the Joint Conference Committee by resolution adopted by the. Organizing Conference on June 4, 1920, in part as follows: RESOLVED, that it is the sense of this Organizing Conference that the Joint Conference Committee should be entrusted with making provision for putting the conclusions of this Conference of engineers into effect, etc. Pursuant to this authority, the Joint Conference, Committee has acted as an Ad-interim Committee has- prepared, a synopsis of the proceedings of the Organizing .Conference, has edited and published the Constitution and By-Laws adopted by this Conference, and. has issued an invitation to become Charter Members of The Federated, American Engineering Societies; to the list of organizations to whom invitations had been extended to attend 'the Organizing., Conference. The Committee in connection with this invitation offered to the extent of its ability, such assistance as might be-desired; and arranged in many cases for one or more of its members to be present when the matter of membership in The Federated American Engineering Societies was considered. . .

Jan 1, 1920

By R. L. Mauger, P. E. Damon, B. J. Giletti

This report includes the lead isotopic dating of a suite of galenas from Arizona and an application of the K-Ar method to the dating of a Laramide porphyry copper deposit, the Silver Bell Mining District. The lead isotopic data supports prior age assignments based upon geologic inference. The Silver Bell study illustrates the necessity of correlative geologic and petrographic investigations for the interpretation of the results of potassium-argon dating. LEAD ISOTOPIC DATING OF GALENAS FROM ARIZONA ORE DEPOSITS A group of galenas from Arizona ore deposits have been analyzed for lead isotope ratios. The results were used to calculate model ages by the. method of Russell, Stanton and Farquhar,l6 in which the age is calculated directly from the Pb206/Pb207 ratio. The use of Pb206/Pb207 ratios eliminates the errors inherent in measuring the abundance of Pb204. The Holmes-Houtermanns model is the other model commonly used for calculating model ages. Both models assume that any lead sample is composed of primeval and radiogenic components and the calculated age is the time at which the lead was extracted from its source area. Using the Holmes-Houtermanns model, a lead is ordinary if its isotopic ratios lie on an isochron. The growth curve that passes through the experimental point determines the U/Pb ratio in the source area. The RSF model assumes the source area for conformable leads is the mantle, that this has a uniform U/Pb ratio, and thus all ordinary leads must lie on a single growth curve, having a mantle U/Pb ratio. The definition of an ordinary lead differs between the models, and differences in age arise mainly from the assumptions made to evaluate parameters in the model equations. These assumptions depend on the hypothesis chosen to explain ore genesis. In the RSF Model, the Pb206/Pb207 ratio is derived as a function of time. The equation contains three undetermined parameters which are evaluated by assuming three known points lie on the curve. These are the following: 1) Primeval lead from the Canyon Diablo and Henbury meteorites, 2) Modern conformable leads which lie on Patterson's zero isochron, 3) Lead from the Bathurst, New Brunswick base metal deposits. The Bathurst deposits are postulated to be examples of "conformable base metal deposits", as proposed by Stanton.l9 A conformable deposit has a particular genetic history and, as a result, the orebody conforms to stratigraphic layering in the host rock. The metals are brought to the surface in volcanic rocks which originated in the mantle. Weathering products of these rocks, including sulfur and metals, accumulate in areas undergoing sedimentation. The formation of sulfide ion in the sediments by the action of sulfate reducing bacteria causes fixation of iron as pyrite. If the pyrite becomes concentrated in favorable stratigraphic horizons, any base metal deposit eventually formed by replacement of pyrite will have a strata bound character. Compaction and expulsion of pore water from the sediments at depth result in upward mobility of solutions containing soluble base metal chlorides. The strata with high pyrite content act as chemical traps for the base metal ions and replacement occurs. An important result of this general evolutionary model is that, if complete separation of lead and parent isotopes occurred during accumulation of the sediments, any ore deposit formed solely of metals derived from those sedimentary rocks will contain "conformable" lead. This would be true even if the actual ore deposit were formed at a later date by some epigenetic process. In this case, mineralization would be controlled by local conditions, and need not conform to stratigraphic layering. Also, any ore deposit containing lead derived from a mantle or mantle-like source, even though not conformable in Stanton's sense, will fall on the curve for conformable ores and thus give a meaningful model age. Model ages for Arizona galena deposits are listed in Table 1. Fig. 1 is a location map. Jerome-Humbolt District: Galenas from the United Verde mine at Jerome and the Iron King mine at Humbolt give model ages of 1750 m.y. and 1640 m.y. respectively. Both deposits are massive sulfide bodies in a host rock of older Precambrian

Jan 1, 1965

By H. D. Merchant

NUMEROUS publications have examined hot hardness of metals and alloys. Some have studied creep in long-time hardness tests, few of which, however, were tested under a spherical indentor. 1-3 The results of Mulhearn and Tabor' indicate a parabolic-type creep for indium and lead, whereas Moore and Tabor2 how a logarithmic-type creep for indium. Similar semilog relationships between hardness and time have been found by Goffard and wheeler3 for magnesium, aluminum, and their alloys. In this note, the elevated-temperature hardness of some complex alloys, shown in Table I, was examined to discover whether any basic information about the deformation behavior of the alloys could be obtained. One of the alloys, H-13 alloy steel, was tested for short-time creep tests to examine the hardness-time relationship at various temperatures. A standard Brinell Hardness Tester, mounted with an appropriate furnace and 99 pct A12O3 poly-crystalline indentor, was employed for the purpose. The alloys were tested at temperatures from room to 1400°F for 30 sec under 1500-kg load. The creep studies were conducted for about 8500 sec at 7l°, 500°, 1000°, and 1200°F. For constants A and B, a relationship of the type H = Aexp(-BT) [ll was obtained for all alloys between hardness, H, and temperature, T. In the semilogarithmic plot, the data points for each alloy were arranged into two groups, each group on a straight line with a specific set of A and B values. These results are in agreement with many such observations on hot hardness, notably those of Westbrook for pure metals,4 The thermal softening coefficient, B, and transition temperature, Tt, for various alloys are shown in Table I. The change in slope around the transition temperature suggests an apparent change in the mechanism of deformation, probably from the shear (below Tt) to the diffusion type of mechanism. At the temperatures above Tt, for constants A' and B, a relationship of the type was obtained between H and T, Fig. 1. The nature of the equation, where R is gas constant, suggests the possibility of a thermally activated mechanism of deformation above Tt. The constant B' may hence be defined as the apparent activation energy of indentation. The B' values of various alloys are shown in Table I. A plot of B vs B' gives a curvilinear relation shown in Fig. 2. The indentation-creep data for H-13 alloy steel is shown in Fig. 3. At 71" and 500°F, the creep initially follows the logarithmic time law. However, the indentation size stabilizes after 7 sec at 71°F, and after 10 sec at 500°F. Further increase in loading time has no effect on indentation size. The creep of 1000° and 1200°F follows the logarithmic time law for the first 1000 sec, after which the

Jan 1, 1964

By Edward Hart

The specimen of glazy iron used for analysis was highly characteristic in appearance. It was made at one of the furnaces of the Glendon Iron Works, working a light burden of ore with a highly silicious cinder. There are very few records of analyses of this variety of iron. I have been able to find but the two given by Bell, and I add these to my analysis for comparison. Bell. 1. 2. Iron,......89.47* 88.18 90.70 Carbon, combined,.... 0.00 0.79 0.71 Graphite,......2.88 2.59 2 68 Silicon,......5.47 5 13 5.13 Manganese,.....1.54 0.77 0.56 Sulphur,......0.04 0.17 0.23 Phosphorus,.....0.60 1.12 1.12 Titanium,.....- 0.26 0.18 Calcium,......0.00 0.22 0.20 Magnesium,.....0.00 0.06 0.03 100.00 9929 101.54

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 E. A. Anderson, P. W. Ramsey, E. J. Boyle

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By P. W. Ramsey, E. J. Boyle, E. A. Anderson

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By O. F. Walker, W. C. Hahn, V. A. Johnson, J. D. Wood

The diffusion coefficients of zinc in single-crystal zinc and carbon in single-crystal and poly crystalline nickel were measured by means of radioactive tracer techniques both with and without the application of ultrasonic vibrations under conditions such that the temperature of the sample was closely controlled. The results of this investigation indicate no enhancement of diffusion in any of the samples. It is suggested that previously reported enhancement may have been due either solely to temperature increases caused by ultrasonic vibrations or in combination with changes in the boundary conditions. A number of observations have been reported in the literature in which it has been implied or inferred that the application of ultrasonics enhances diffusion (see, for example, Refs. 1-5). The present study was undertaken in an attempt to observe this effect under carefully controlled conditions, particularly with regard to measurement and control of the temperature of the sample. Two different types of systems were studied; these were the self-diffusion of zinc and the diffusion of carbon in nickel. EXPERIMENTAL For diffusion with ultrasonic energy applied, the samples were included as part of a resonant ultrasonic system operating at 58.5 kcps. The ultrasonic generators used were rated at 100 and 250 w and could be tuned over a frequency from 10 to 100 kc. A PZT (lead titanate/lead zirconate) ceramic transducer provided the driving vibration. This system requires no metallurgical joining of the specimen to the acoustical transmission line since the ultrasonic driver and the follow-up section clamp the specimen in position by means of a constant pressure of 50 lb developed by an air cylinder. The ultrasonic driver and follow-up section, both made of titanium, were 4 in. in length from clamping point to the end in contact with the specimen. Using the relationship given by Mason,6 A = V/f, the resonant wavelength, A, in titanium is calculated to be 3.3 in. at a frequency, f, of 58.5 kc, taking the velocity of sound in titanium, V, as 1.95 X 105 in. per sec. The 4-in. driver and follow-up section, therefore, are each 4.0/3.3 =1.21 times the resonant wavelength. Clamping pressure must be applied at stress nodes of the transmission line in order to preserve resonance. Therefore, a specimen length of 0.58 times the wavelength in the specimen was required to place the clamping pressure application points at stress nodes exactly three wavelengths apart. A stress antinode was contained in the center 3 in. of the specimen. A small PZT ceramic disc attached to the follow-up section provided an output voltage proportional to the intensity of the standing wave. This output voltage was monitored on an oscilloscope and the ultrasonic system was tuned to resonance by varying the frequency until the output signal was a maximum amplitude. The amplitude of the output signal was maintained constant throughout the diffusion anneal. A split cylindrical stainless-steel chamber, which was purged with argon prior to and during the runs, was placed around the specimen. The chamber in turn was surrounded by a movable furnace whose temperature could be controlled to 7C. Heat exchangers were used to cool the driver, follow-up section, and ultrasonic transducer. Great care was taken to obtain the true specimen temperature in all cases. Several different methods were tried; the most successful was that in which the thermocouple was held in contact with the midlength of the specimen by means of an asbestos insulating pad and wire straps. In the case of zinc, single-crystal specimens of 99.999 pct purity were used. The samples were 0.25 by 0.25 in. square and of the proper length for resonance, that is 1.1 in. long with the c axis parallel to the long dimension of the specimen for the case of diffusion perpendicular to the c axis and ultrasonic motion parallel to the c axis, and 1.9 in. long with the c axis perpendicular to the long dimension of the specimen for the case of diffusion parallel to the c axis and ultrasonic motion perpendicular to the c axis. In each case, one of the rectangular faces was electroplated with a thin film of zinc containing Zn The constant pressure used to clamp the specimen in place in the ultrasonic system caused some deformation in some of the samples. For these samples the deformation was concentrated in either end of the specimen; thus, for all samples (both zinc and nickel) the center in. was cut from the specimen after the diffusion anneal to be used for sectioning and counting. The nickel single-crystal samples, of 99.999 pct purity, were used in the form of rods 0.25 by 0.187 by 2.07 in. long with the (100) direction parallel to the rod axis. The polycrystalline nickel samples of 99.97 pct purity had an average grain diameter of 0.007 in. and were used in the form of rods 0.25 by 0.125 by 1.87 in. long. The direction of ultrasonic motion was parallel to (100) direction (bar axis) for the single-cqstal samples and parallel to the bar axis for the polycrystalline specimens. A thin film of c14 suspended in methanol was applied to the diffusing face of the specimen. Two specimens were butted together lengthwise for each diffusion anneal to minimize oxidation. After diffusion, a precision lapping device similar to the one described by Goldstein7 and a radiation detector were used to obtain a plot of specific activity vs penetration distance for each specimen. (A scintil-

Jan 1, 1969

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

By C. E. Tsoutrelis

A new method for determining rock drillability in diamond drilling is discussed; the method takes into consideration both penetration rate and bit wear. The method is based on drilling a rock specimen under controlled laboratory conditions using a model bit. The technique used for determining the experimental variables is extremely simple, quick, and reliable. Drillability is then determined by the mathematics of drilling. In considering the different factors that affect diamond drilling performance, the nature of the rock to be drilled is of outmost importance since it affects significantly the drilling costs and such other variables as bit type and design, drilling thrust, and bit rotary speed. Many attempts have been made to study this effect by correlating actual drilling performances either to certain physical properties of the rock being drilled1-? or to test drilling data obtained under laboratory conditions.7-13 These attempts were aimed at providing a reliable method of predicting by simple means the expected rock behavior in actual drilling, thus giving the engineer a tool to use in estimating drilling performances and costs in different types of rock. The purpose of this paper is to describe such a method by which rock drillability (a term used in the technical literature to describe rock behavior in drilling) could be determined in diamond drilling. It is believed that the proposed simple and reliable method will cover the need of the mining industry for a workable method of measuring the drillability of rocks. It should be emphasized, however, that since drill-ability depends on the physical properties of rock and each drilling process (diamond, percussive, rotary) is affected by different or partly different rock properties,14-l6 the proposed method of determining rock drillability cannot be extended to the other drilling processes. The results presented in this paper form part of an extensive three-year research program carried out by the author in the laboratories of the Greek Institute of Geology and Subsurface Research. During this period the effects of the physical properties of rocks and of such operational variables as drilling thrust and bit rotary speed in diamond drilling were investigated in detail. DRILLABILITY CONCEPT The literature is not devoid of drillability studies. While there are a number of investigators1,3,5-7,9-0,12-13,17 who have attempted to establish by direct methods (i.e., drilling tests under laboratory conditions) or indirect (i.e., through a physical property of rock) an index from which the drilling performance in a given rock may be estimated, very few6-7,9,12, of the proposed methods seem to be of much practical value to the diamond drilling engineer and none to date has been universally accepted. Commenting on the proposed methods for assessing rock drillability, Fish14 remarks that "for a measure of drillability to be accepted it is essential that penetration rate at a given thrust and bit life are elucidated as otherwise the method is of little value." This statement should be examined in more detail by making use of the penetration rate-drilling time diagram obtained in drilling a rock under constant operational conditions. Furthermore, the merits of using this diagram to describe rock drillability will be pointed out. At the same time reference will be made to this diagram when discussing some previously proposed methods. Fig. 1 illustrates such a diagram for three rocks,A, B, and C, which have been diamond drilled under identical conditions. It is assumed here that rocks A and B have the same initial penetration rate, i.e., VOA = Vog, but since rock B is more abrasive than A, rapid bit wear occurs and as a result the fall of its penetration rate with respect to time is more vigorous than in rock A. This is shown graphically by a steeper V = f(t) (0 curve in this rock than in rock A. Rock C has a lower initial penetration rate, due to higher strength properties16 but since it is not very abrasive, only a slight fall of its penetration rate occurs during drilling (in this category are some limestone and marbles with compressive strength above 1000 kg per sq cm). It follows from the foregoing considerations that the characteristic for each rock curve (I) is a function of (i), the penetration rate of the rock Vo recorded at the instant of commencing drilling, which determines the starting point of the curve (1) on the y-axis and (ii), the abrasive rock properties which determine the rate of fall of Vo with respect to time. Thus, curve (I) provides an actual picture of the rock behavior in drilling for given operational conditions, and it can be used with complete satisfaction to assess rock drillability. It can be seen clearly from Fig. I that proposed methods for assessing rock drillability by measuring the

Jan 1, 1970

By W. T. Isbell

Although the pressure to meet the heavy demand for lead still took precedence over new metallurgical developments in the field of roasting, smelting, and refining of lead in 1948 there nevertheless has been considerable activity in the experimental development of new processes and improvements as well as plans for the modernization of many plants both here and abroad. Increasing labor and material costs have stimulated the trend to greater mechanization, revamping of flow sheets, and construction of larger units wherever possible. Although there have been many serious labor stoppages in the United States, Mexico, and Europe, labor supply has improved in most plants even if it has fallen off in efficiency.

Jan 1, 1949

NEW MEMBERS The following list comprises the, names of those persons who became members during the period June 10 to July 10, 1914: Members ALDRICH, HAROLD W., Supt. of Leaching Plant, Washoe Red. Wks., Anaconda Copper Co., Anaconda, Mont. AYER, FRANK ASHTON, Mine Foreman.. ..Detroit Copper Co., Morenci, Ariz. BELL, ARTHUR F. L., Chief Engr., Associated Oil Co.., 817 Sharon Bldg., San Francisco, Cal. BERGMAN, JULIUS GUSTAF, Mech. Engr., Chief Draftsman, Arizona Copper Co. Morenci, Ariz. BURT, CURTIS F., Min. Engr., Pittsburg-Dolores Mining Co., Rockland, via Yerington, Nev. CALLAWAY SCOTT DAVID, Chem La Harpe Smelter Co., La Harpe, Kan. CAMPBELL, W. C., Min. Engr 4 Princess St., Roodeport, Transvaal, So. Af. CARROLL, GEORGE A., Genl. Mgr Kildare Min. Co., Manson, B. C., Canada. CARUTHERS, JOHN LYTLE, Min. Engr., Asst. Engr., St. Louis, Rocky Mountain & Pacific Co.. Raton. N. M.

Jan 8, 1914