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By P. R. Swann, J. G. Parr

Quenched structures were studied in alloys containing up to 12.5 pct cobalt. The subsequent decomposition of a 10 pct cobalt retained-ß phase alloy was investigated using metallographic and X-ray diffraction methods. Hardness measurements also were made during the decomposition process. Precipitation of Ti2Co is by nucleation and growth; and an activation energy of 50,000 cal per mole was determined. The values of the coefficient ß suggest that the precipitate is pearlitic at temperatures between 450 and 475°C, and spheroidal between 500 and 525°C. THIS paper describes part of a series of invesligations into phase transformations in binary alloys of titanium with transition elements. The general approach is similar to that taken in work on titanium-iron and titanium-nickel alloys.' Previous investigators'' have established the titanium-rich end of the titanium-cobalt phase diagram, reproduced in Fig. 1. Orrell and Fontana' showed that alloys containing more than about 6 pct" cobalt quenched from the ß range, produced 100 pcl retained-p phase. The isothermal decomposition of alloys containing between 0.8 pct Co and 15.5 pct CO was investigated by the same workers in the temperature range 650 to 1000°C. They reported that these alloys transformed into a or Ti,Co depending on the cobalt content, but no quantitative data were given. In the work to be described a series of alloys containing 0.8 pct Co to 12.5 pct Co was examined in the quenched condition. The 10 pct Co alloy (the lowest cobalt content to retain 100 pct ß on quenching) was selected for further work on the tempering kinetics of the ß decomposition. Experimental Procedure Since our own melting equipment was not installed at the outset of this work, the Physical Metallurgy Division of the Department of Mines and Technical Surveys (Ottawa, Canada) prepared the alloys. These were made of Japanese sponge, (which when melted had a value of 103 DPH, using a 1-kg load), and electrolytically prepared cobalt. The al- loys, made up to contain 0.8, 1.6, 3.3, 5.8, 8.3, 10.0 and 12.5 pct Co, were homogenized by swaging into rods at 900°C. Filings were taken from the rods, and any iron chips from the file were separated magnetically. Size fractions of both plus and minus 200 mesh (about 75p) were shown by their constitution, after annealing just below the eutectoid temperature, to contain the same cobalt content. Consequently, it was permissible to use the —200-mesh fraction, knowing it to be representative of the rod composition. Quenching in argon was carried out in a newly designed furnace, whose features include (1) an Inconel furnace tube, (2) a positive pressure of argon maintained at all times in the furnace—even when a sample is removed or inserted. The furnace is shown in Fig. 2 and is described in the Appendix. The tempering processes were carried out on powder samples sealed in evacuated quartz capsules. Since the highest tempering temperature was 525OC, no protection against reaction with the quartz was necessary. (Tests were made on filings of iodide titanium and showed no hardness increase after equivalent heat-treatments.) A thermocouple was attached to the capsule, which was heated to the

Jan 1, 1959

By H. D. Kessler, M. Hansen, R. J. Van Thyne

The phase diagram of the titanium-rich portion of the system Ti-Cr-Fe to 70 pct Ti was established by means of isothermal sections at 900°, 800°, 750°, 700°, 650°, 600°, and 550°C, using arc-cast alloys. An isotherm at 800°C was determined for the section bounded by Ti, TiFe2, and TiCr2. Micrographic analysis was employed as the principal method of investigation, supplemented by X-ray diffraction and incipient melting studies. A ternary eutectoid, ß ? a+ TiCr2 + TiFe, occurs at approximately 8 wt pct Cr, 13 wt pct Fe, and about 540°C. AMONG the first titanium-base alloys in commercial production were the Ti-Cr-Fe alloys. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the system. No information on the constitution of the titanium-rich corner was available. Vogel and Wenderott studied titanium-poor ternary alloys.' As part of this program, the binary systems Ti-Cr and Ti-Fe have been determined previously by the authors.' Other investigators have also studied the binary systems Ti-Cr,3-7' Ti-Fe.³,8-10 Both of the binary systems are characterized by the eutectoid decomposition of the ß phase. Most of the effort of the present work has been concentrated on the titanium-rich corner with compositions of less than 30 pct total chromium and iron content. The determination of isothermal sections was the experimental approach used to obtain the ternary phase diagram. Vertical sections were used to check the consistency of the isothermal sections. While this investigation was in progress, a study of the Ti-Mo-Cr system at Armour Research Foundation disclosed the existence of a high temperature modification of TiCr2 above 1300 °C.11 This allotrope has a hexagonal structure of the MgZn2 type, iso-morphous with TiFe2, whereas the low temperature modification of TiCr2 is cubic," of the MgCu2 type. The existence of allotropy in TiCr2 of course means a more complicated set of phase relationships in this general region than if the phase were monomorphic, as was first assumed. Additional studies were made late in the investigation in order to clarify the part that the hexagonal TiCr2 phase plays in the ternary phase relationships. These will be discussed in a separate section. Because they are of greatest practical significance, the phase relationships in the titanium-rich corner will be presented first, omitting the equilibria involving the hexagonal modification of TiCr2 in an effort to simplify the presentation somewhat. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9 pct pure) produced by the New Jersey Zinc Co. High purity chromium and iron were obtained from the National Research Corp. Table I gives the analyses of these materials. Melting Practice: Over 100 alloy ingots weighing 10 to 20 g were melted in a nonconsumable electrode arc-melting furnace. As the techniques are identical to those reported previously,12,13 they will not be detailed here. The ingots were melted in the cavity of a copper melting block insert under a slight positive pressure of helium. No measurable hardness

Jan 1, 1954

By Richard P. Rothwell

Fires in mines are so serious in their consequences and of such frequent occurrence, that their causes and the means of extinguishing them are certainly questions of the greatest interest to a large part of the engineering profession. We have already, in this country, many mines which have been burning for years, and though our hard anthracite is so difficult to ignite that for a quarter of a century after it was first discovered it mas not known how to burn it except with the aid of an artificial blast, yet most of the fires which have occurred underground have been in anthracite mines, and in the coal itself. The injury which these fires have caused to properties in various parts of the anthracite regions, and the cost of extinguishing them, would amount to many millions of dollars, and they have also occasioned the loss of many valuable lives. It is not surprising, therefore, that the subject has already attracted much attention, and the exercise of great ingenuity; and the present communication is made less with the expectation of announcing anything new, than with the object of putting upon record the present state of our knowledge on this subject, or, in other words, of indicating how defective are the present means of combating underground conflagrations. Causes of Mine Fires.—Even upon the surface, fire is a terrible foe to contend with, and there is probably no other which inspires such thorough and well-founded alarm. With what feelings, then, must we look upon this destructive element, when its field is in the narrow galleries of a mine, where the poisonous products of combustion, spreading in every direction, protect, in the most effectual manner, the fire itself from the attacks of extinguishers, while, if the face of attack be ventilated so as to enable then] to approach the seat of the fire, the air current simply increases the extent and violence of the conflagration. Fires underground originate in as various ways as those on the surface, and it is scarcely necessary to say that, except in the rare cases where they are the result of design, they are invariably classed as " accidents," and most generally as " unavoidable accidents." In reality, by an intelligent understanding of their causes and with due precautions, they can almost always be prevented. Ignorance and

By Julian Kennedy

When it was decided to erect these furnaces the company also decided to use the Cowper type of stoves. It was, however, desirable to improve upon the plan of the stoves then in operation, to avoid, if possible, some defects which had shown themselves in them. The stoves now in use at Furnaces " A," " B," and " C " are of the well-known type of Cowper stove, having a circular combustionchamber placed at one side of the stove, and a regencrator with crescent-shaped section, resting at the bottom oil cast-iron glatings, which are supported in turn by cast-iron girders, the products of combustion passing up the chamber, down through the flues of the regenerator, and thence to the chimney. The objection to this shape of stove, that the gases would not pass down the parts of regenerator lying beside and behind the combustion-chamber—the horns of the crescent, as it were,—did not apply to the newer form of stoves, with combustion-chamber having a straight wall next to the regenerator; but. there were other defects, the principal ones bring the small size of the openings through the regenerator and the material used for supporting it. The small passages (4" X 4") soon choked up, and when a part of them became entirely closed, not only was the effective heating surface greatly diminished, but as the remaining opening were not sufficient to absorb the heat

Jan 1, 1882

By Robert A. Cook

In the increasing struggle to cheapen the cost of our iron and steel products a great deal of attention lias been given to economies in the manufacture of coke; and while but little lias been accomplished in this direction in the United States, the narrow margin between cost and market-price, which has obtained here for the past few years of continuing manufactur ing depression, has brought the coke-maker face to face with the problem, how to save, and benefit by it, the hitherto waste products of distillation. I These may be summed up under three heads, generally rank ing, in value, in the following order: 1. Ammonia salts.. 2. Oil- or tar-products. 3. Gas. There are cases in which the last may assume the position of greatest importance. The greatest obstacle encountered by the American coke maker, on investigating the subject, has been the apparent necessity of discarding his existing plant of bee-hive ovens, and erecting an entirely new and very expensive system of retort ovens, against the product of which Be has probably been prejudiced from his earliest knowledge of the subject. The object of this paper is to bring prominently before our coke-experts a brief history of the development at Sheffield, England, of a most successful system of the utilization of by products in connection with all already existing plant of bee hive ovens. This system has now been in satisfactory operation for about five years, and is applied to a series of blocks of ovens, comprising-about 140- in all At this plant, belonging to the well-known firm of Newton,

Jan 1, 1897

By T. S. Maio, J. G. Mansanti

In 1978, Ozark Lead Co. made the decision to expand the capacity of its mine/mill complex by 33%. The objectives of the expansion were to increase mine production capacity by 1.8 kt/d (2000 stpd), increase lead metal production by 21.8 kt/a (24,000 stpy), and to construct new facilities and modify existing equipment to accommodate increased production. This paper gives a brief explanation of the equipment installed and the overall production and metallurgical benefits realized from this expansion. The expansion was completed in the second half of 1980 with all equipment debugging and fine tuning completed by the first quarter of 1981. Concentrator modifications and improvements were basically restricted to four areas: materials handling, automation of the mill grinding circuit, increased flotation capacity, and concentrate dewatering.

Jan 1, 1985

G. M. TAYLOR,* Colorado Springs, Co1o.-I do not think the plan outlined in this paper would work at Cripple Creek. Most of our men have had a pretty good education. The Cripple Creek district is a lessee district-I do not think there is one mine operating in Cripple Creek to-day that does not have the leasing system. We have as many men leasing on our property as we have mining and every plan who is working for wages is looking for n lease-everyman has mined for him- self, he has been his on7n boss on n lease, either on our own property or

Jan 1, 1919

By F. W. Glaser

Metal-carbon-boron powder mixtures were hot pressed and the resulting specimens were studied by X-ray diffraction. It was found that regardless of the starting combination of the metal, carbon, or boron powders, a metal boride phase was always the major component in these samples. In the absence of carbon the boride phase formed on hot pressing depended only on the amount of boron present. Two new phases of the system Ti-B were found. They are Ti2B and Ti2B5. The existence of a controversial face-centered cubic phase of formula TiB was confirmed. Electrical resistivities were measured for various boride phases. It was found that the diborides are generally better conductors than the monoborides of the same metal. THE carbides and borides of the transition elements have very high melting points, in the range 2500° to 4000°C, and are therefore of interest as high temperature materials. The literature on the stability or chemical reactivity of these carbides and borides is very scarce. Various investigators'-" have demonstrated a relative instability of certain carbide phases in the presence of boron or boron-containing substances. In a recent publication, Glaserl demonstrated the stability of zirconium-boride (ZrB,) in the presence of carbon at temperatures in excess of approximately 2900°C, while during a preliminary investigation of boride phases, Steinitz' concluded that the diborides are stable in the presence of carbon while the monoborides of the fourth and fifth group are not, forming diborides plus carbides instead. Nelson, Willmore, and Womeldorph" have elaborated on the reaction B,C + 2TiC = 2TiB, + 3C, which was known to occur because of a relative instability of B,C and the great tendency towards TiB, formation at relatively low temperatures (approximately 1200°C). A similar study, involving as starting materials TiO, and B,C and resulting in TiB,, was recently described by Honak4, who observed the beginning of an exothermic reaction of a Ti0,-B,C powder mixture, which, when preheated in a hydrogen atmosphere to approximately 950°C, was carried to about 1600 °C by the heat of reaction. To shed more light on reactions of this type (Metal-C-B), the final product apparently always resulting in a boride phase at the expense of a carbide phase," a systematic investigation was started * Boride phases of various metals, as reported to date, are listed in Table I. and the following is an account of some of the results that were obtained. Materials, Preparation of Samples, Testing Methods The raw materials employed for this work consisted of various carbide, boride, and metal powders. as well as of boron and graphite powders. In cases where commercial grades of carbides were considered unsuitable because of low purity or excessive amounts of graphitic carbon, such carbide powders were prepared by this laboratory. The procedure for the preparation of carbide powders (zirconium carbide, titanium carbide, tantalum carbide, and niobium carbide) consisted of mixing graphite and the respective metal hydride powders in stoichio-metric proportions and subsequent heating of such mixtures in a hydrogen atmosphere in carbon crucibles. The heating was by high frequency to temperatures ranging between 1700" and 2100°C. The resulting carbide was then comminuted and screened to the desired particle size. ZrB, and TiB, powders were produced by the electrolysis of fused salt baths, according to the method described by Andriex.. The borides of niobium, vanadium, tantalum, molybdenum, chro-ium, and iron were obtained by mixing the respective metal and boron powders in the desired proportions. Such metal-boron mixtures were heated in a high frequency furnace to form boride powders. For each metal-carbon-boron group (Tables I1 through XI) a metal, its hydride, carbide or boride were mixed with carbon, boron or boron carbide powders. The additions of carbon, boron or boron carbide powders to any of these metals or metal compounds were calculated to satisfy a particular carbide or boride phase that according to the literature (Table I) had definitely been established by X-ray diffraction work. Samples of powder mixtures were hot pressed in graphite molds that were heated by direct conduction. The specimen dimensions were approximately 2.5X1X1 cm. Hot pressing temperatures were measured optically and maintained for approximately 30 sec under a constant pressure of about 1.3 ton per sq in. Wherever possible, an attempt to obtain maximum specimen density was made by temperature variation. Electrical resistivity testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp, at room temperature. To obtain electrical resistivities for specific carbide or boride phases, values were plotted as a function of the respective sample densities

Jan 1, 1953

By A. H. Smallbone, R. Lathe

Considerable efforts have been expended to apply multiple regression techniques to quantitative determinations in x-ray fluorescence analysis. Multiple regression has been shown to be an effective method for correlating x-ray fluorescence intensities to elemental concentrations. Although many other techniques have been devised to solve the problem of matrix effects in x-ray fluorescence analysis, there are few as efficient in terms of storage requirement or ease of programming for digital computers as the multiple regression method. In the case of ore slurry, it has the additional advantage of allowing a unified approach to the problems of slurry density correction and matrix effect corrections. The data used in the present work were obtained with an on-stream x-ray analyzer capable of analyzing 15 slurry streams for as many as nine elements simultaneously. One of its fixed monochromators was set to accept scattered radiation at a discretely selected wavelength as a means of monitoring the slurry's pulp density. The data were reduced to obtain the correlation equations and a computer program combining slurry density with matrix corrections was written in FORTRAN IV to calculate concentrations.

Jan 8, 1969

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By Carl E. Swartz

Although a number of articles appeared during the war advocating the use of cadmium in lead-tin solders, very little information of value can be found in the literature regarding the properties of solders containing cadmium. In most of the published articles the cadmium seems to have been considered merely as a partial substitute for tin in a tin-lead alloy rather than as an essential constituent of a ternary alloy. The primary object of the substitution of cadmium for tin was to lessen the amount of tin required, at a time when the latter was scarce and high-priced, and thus to produce a cheaper solder. While this object was accomplished, the new properties resulting from a change from a binary lead-tin alloy to a ternary lead-tin-cadmium alloy were not given proper consideration in many cases. For the past few years, the American Smelting & Refining Co. has been marketing a very considerable amount of cadmium in the form of lead-tin-cadmium alloys for use as solders for certain special purposes, and the successful use of these solders suggested that if more extensive knowledge were available concerning the properties of lead-tin-cadmium alloys of various compositions their field of usefulness might be materially extended. The investigation described in the present paper was undertaken to obtain this information and, by means of tests under conditions approaching those of practical use, to determine the suitability of cadmium solders for various purposes. Characteristics and Requirements of Solders in General General Physical Properties.—When cast into bars, solder should present a smooth and bright appearance free from oxide inclusions and bubbles. Ductility should be as great as possible without sacrificing tensile strength, and vice versa. Hardness and specific gravity are not of any great importance. Melting Characteristics.—The melting or solidification range is important. This statement applies both to the extent of the range and to the actual temperature at which complete solidification occurs. A rather narrow solidification range is desirable in soft solders in order that solidification may take place quickly. The solder should have high fluidity at temperatures only slightly above its melting range. For a

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,' there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By Frank M. Brooks

Endeavoring to meet the requirements of more oil created by the war effort, the oil industry of Kansas in 1944 maintained a level of exploratory and development work well above the average of previous years. During the year, 1866 test wells were drilled, of which 838 were completed as new oil wells, 89 as new gas wells and 939 as dry holes. These figures compare with 895 new oil wells, 32 new gas wells and 834 dry holes for a total of 1761 tests in 1943. Thus, there was a marked decrease in the number of new oil wells, and an increase in the new gas wells and dry holes. The total daily initial potential of production discovered by the successful wells amounted to 494,689 bbl. of oil as compared with 736,297 bbl. in 1943. The increase in unsuccessful tests and decrease in the daily initial potential of production has caused considerable comment and speculation among the oil operators of the state. This tends to confirm the fact that each year it is becoming harder to find the remaining oil fields. The total number of wildcats drilled in Kansas was 651 in 1944, including the so-called "extension wildcats" (more than 1/2 to I mile from known production). Of this number, 410 are classified as "rank wildcats," being more than one mile from production. The total of 651 compares with the total of 577 for 1943, showing an increase in wildcat drilling of 74 test wells: Of these tests, 81 were successful in finding new oil fields or substafitially extending known areas of production, and 20 either found new gas pools or extended old ones. The ratio of dry holes to producing wells among the "rank" wildcats was approximately 10 to I (372 dry and 38 successful). This compares with a ratio of 10 to I in 1943, 11 to I in 1942, and 6 to I in 1941. A compilation of the results obtained by 34 active companies, including all of the major companies, reveals that their efforts accounted for 286 rank wildcat wells, of which-37 found oil or gas, making a dry-hole percentage of 87. Approximately 55 per cent of all, tests (pool and wildcat) were failures. Thc Kansas Nomenclature Committee of the Kansas Geological Society named and classified 43 new oil fields and 8 new gas fields during the year. The discovery wells of the new oil fields had a total initial potential of 18,358 bbl. for a per well average or' 427 bbl. The average initial potential per well in 1942 and 1943 was 894 and 419 bbl., respectively. With nearly all wells producing at their economic capacity, the total production for Kansas during 1944 totaled 101,896,704 bbl., which compares with total runs of 107,709,679 bbl. in 1943. Production of natural gas during 1944 reached a new high record of 135 billion cubic feet. This compares with 122 billion cubic feet for 1943, and 98 1/2 billion cubic feet for 1942. The large Hugoton field of Southwestern Kansas accounted for about half of the total gas produced. Highlights OF the Year Although 51 new fields were found in the state during 1944, it is apparent that the

Jan 1, 1945

By C. H. Cheng, C. E. Birchenall

The fundamental problem in the thermodynamics of solid solutions is the determinatiorl or calculation of the activities of the components as a function of temperature and composition. Since the theory of metals is not suficiently developed to allow a priori calculation of these quantities, they must be obtained from experiment. C. Wagner1 has reviewed the literature of this subject for the period before 1940. Although several important and extensive studies have been made in the meantime, the number of systems to which any sort of quantitative information can be assigned is vanish-ingly small. These data have become of great potential importance in studies of the structure of solid solutions2 and intermetallic compounds, the nature of the diffusion process,3,4 and perhaps even the mechanism of mechanical deformation.5 For these reasons, it. seems very worthwhile to extend the experimental data in this field. Although there is little use in duplicating Wagner's review, attention should be directed to the most recently reported investigations. A brief enumeration of the methods of measurement previously employed also should be valuable. The most direct method is the determination of the partial pressure of the components in the vapor phase in equilibrium with the solution. Both equilibrium and kinetic methods have been tried in metal systems, but almost exclusively on liquid phases. Only in the ease of carbon in iron alloys and in the copper-zinc system have extensive measure- ments been made which include solid phases. When one of the components is an element, such as nitrogen or carbon, which forms compounds which are very volatile and stable at normal temperatures and pressures (CH4, Co2, CO NH3), it is frequently possible to equilibrate mixtures containing these (such as CH4-H2, CO2-CO, NH3-H2) independently with the elernents (C, X) and with the metal (Fe, Ni, etc.). Such measurernents have been made for carbon in iron, iron-silicon, and iron-manganese alloys by Smith6 and in iron and iron-nickel alloys by Toensing.7 Differences between carbon activity values at the same temperature and carbon content when carboil is introduced from CH4-H2 rnixtures or CO-CO. mixtures indicate that the effects of hydrogen and oxygen in the system are not negligible, and one can only hope that the true value lies somewhere between these sets of results, probably nearer the CH4-H2 data since hydrogen is less soluble in iron than oxygen. This is essentially an equilibrium method, although flowing gas is employed. A kirletic method has been employed which consists of sweeping an inert gas (generally hydrogen) over the alloy at a series of rates, condensing the metal vapor out,, and analyzing it. The metal content can be extrapolated to zero flow rate (equilibrium). Wejnarth's8 work on Cd-Mg and Zn-Mg is a good example of this frequently used method. A variant of this consists of equilibrating a known volume of inert gas with the alloy, sweeping it out quickly, and analyzing for metal. In common with the above method, it has the disadvantage that the "inert" gas is generally somewhat soluble in the alloy. Moreover, the former continuously displaces the system from equilihrium and may give low values if solid diffusion is involved. The dew point method applied by Hargreaves9 to the alpha and beta brasses and by Schneider and Stolll0 to A1-Zn avoids the introduction of another component to the system, but is useful only in systems in which one component is much more volatile than the other. The alloy sealed in one end of an evacuated silica tube is heated to the desired temperature. The temperature of the other end is lowered until droplets of the volatile component condense. When the temperature is raised slightly, the droplets will evaporate. By careful adjustment of temperature, the range between evaporation and condensation can be narrowed appreciably. An independent determination of the vapor pressure of the . pure volatile component is necessary to give the partial pressure over the alloy. This is the method employed here to determine the vapor pressures of zinc and cadmium over their silver alloys up to 34 pct in cadmium and 76 pct in zinc. The former involves only the a solid solution, but the latter covers the a, ß, y, and e fields. In recent determinations, Herbenar, Siebert, and Duffenbarkl1 used the

Jan 1, 1950

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942

By Earl Oliver

SEVERAL notable papers, and free discussion on many controversial subjects, marked the various sessions of the Petroleum Division at the annual meeting. The Division first convened on Tuesday afternoon, Feb. 16, and wound up with a dinner and technical meeting on Thursday night. H. C. Fowler presided at the opening session, which was devoted to problems of engineering research and production engineering. Joseph Chalmers abstracted his paper on the flow of air and gas through porous media, in the preparation of which E. L Rawlins and D. B. Talia-ferro contributed. G. H. Fancher told how much he and his associates at Pennsylvania State College were interested in this field, and described the problems they had met in conducting test work. He made a plea for standardization of testing methods. Mr. Fowler then read an abstract of written discussion by Professor Barb, which was followed by discussion by Dr. Fancher and Mr. Chalmers of technical points in connection with the Chalmers' paper. H. H. Hill abstracted written discussion from Messrs. Wilde and Moore, of the Humble company. The second paper, by K. B. Nowels, on computing pressure drop in the pipe of flowing oil wells, was abstracted by the author. Messrs. Blair Smith, G. W. Coggeshall, and I. I. Gardescu participated in the discussion, and the chairman abstracted written discussion prepared by Mr. Rawlins. Most of this had to do with the viscosity of gas¬oil mixtures, on which subject Mr. Nowels said there was great need of accurate technical information.

Jan 1, 1932

For the third year in a row total value of the Nation's mineral production broke all previous records. A new peak of $20.4 billion was reached in 1964. So says the U. S. Bureau of Mines. The Bureau's preliminary estimate for 1964 is $800 million higher than the value reported for 1963, and $1.6 billion greater than the 1962 figure. The unprecedented demand for minerals, has stimulated development of new mines and expansion of processing capacity in many parts of the country.

Jan 2, 1965

By B. C. Burgess

AFTER many years of close and friendly association with talc and soap-stone, this orthographically distinguished mineral steps forth in this edition, for the first time in a chapter of its own. Pyr, the Greek for fire, and phyllite, a rock or stone, form its name and at the same time refer to the first recorded use of pyrophyllite as firestones or hearthstones. Another derivation of "phyllite" is from the Greek phyllites, "of leaves," alluding to the beautiful white radial crystal aggregates that form when pyrophyllite is heated. Pyrophyllite used by the Chinese for carving is called agalmatolite, from the Greek agolma, meaning an image. COMPOSITION AND PROPERTIES Pyrophyllite has previously been grouped with talc because of the close similarity of the minerals in physical and optical properties. They have the same space group; and chemically they are closely related, pyrophyllite being the aluminum silicate A12Si4010(OH)2 and talc the magnesium silicate Mg3Si4010 (OH) 2. Another arrangement of the pyrophyllite formula is generally given as A12034Si02H20 because it expresses the chemical composition as usually determined (alumina 28.3 pct, silica 66.7 pct, water 5.0 pct). Vanderbilt gives pH values of pyrophyllite 5.6 to 8.4.29 Pyrophyllite usually is white, pale green, cream or pale yellow, buff or light gray. It is found in darker shades and other colors principally due to oxidation of contained iron minerals. It is translucent in thin sections. In hardness it is 1 to 2 in the Mohs scale. Its specific gravity is 2.8 to 2.9. In bulk specific gravity, the powdered mineral ranges from 0.4 to 0.7. Its luster is pearly to dull; it is infusible in the Bunsen burner flame, slightly affected by aqueous solutions of sodium carbonate and hydrochloric acid. It is decomposed by sulphuric acid, with separation of gelatinous silica. It is characterized chiefly by its micaceous structure and cleavage, its softness and greasy feel. Two other varieties occur

Jan 1, 1949