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By K. A. Jackson

An analysis of the conditiom fm the dendrite-eutec-tic transition is presented which takes into account a temperature gradient. The composition and temperature in the liquid ahead of a eutectic interface growing at a particular velocity are used to determine whether dendrites can grow faster than the eutectic interface in the liquid which exists ahead of it. If the dendrites grow faster, then a mixed structure with dendrites growing ahead of the eutectic interface is expected. If the dendrites do not grow faster, then only eutectic will be present. The analysis is presented for Sn-Pb system, for which sufficient experimental data to make the analysis are available. The transition from eutectic to dendrites-plus-eutectic derived by this analysis is in good agreement with the recent experimental observations of Mollard and Flemings on Sn-Pb alloys. In alloys which grow with a lamellar eutectic structure, the lamellar structure can be grown over some range of compositions close to the eutectic composition. When the composition is too far from the eutectic composition, dendrites of one or another of the primary phases grow ahead of the eutectic interface, producing a microstructure consisting of "primary phase" interspersed with a lamellar eutectic. Hunt and Jackson' have recently predicted the range of compositions over which the eutectic phase should grow in Sn-Pb alloys, and the composition-growth rate dependence of the transition from eutectic to dendrites-plus-eutectic. This prediction was based on work on organic eutectics. The model on which the prediction was based assumed that there was no temperature gradient in the system, a condition approximately satisfied in the study of organic eutectics2-5 but not in the growth of metallic alloys. Mollard and Flemings6,7 have recently reported experimental results for Sn-Pb alloys in which they have located the transition from eutectic to eutectic-plus-dendritic growth. The experiments were performed using large temperature gradients (65 to 515 deg per cm), so that the assumption of zero gradient on which the predictions of Hunt and Jackson' were based does not apply. It is not surprising therefore that the predictions' were not born out by the experiments.7 In the present work, a modification of the model used by Hunt and Jackson is presented which takes into account the temperature gradient. The modified form of the theory predicts the transition from eutectic to eutectic-plus-dendritic growth in terms of the composition, growth rate, and temperature gradient. Good agreement with the experimental data of Mollard and Flemings7 is obtained. THE HUNT-JACKSON MODEL The model used by Hunt and Jackson' to predict the transition from eutectic to eutectic-plus-dendritic growth was based on the assumption that dendrites grow ahead of a eutectic interface only if they grow faster than the eutectic interface. Analytic expressions for the growth rate of dendrites and the eutectic in Sn-Pb alloys were obtained by fitting experimental data with equations whose form was indicated by theory.

Jan 1, 1969

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By G. C. Gardner

A new correlation of blast penetration in model and operating blast furnaces is presented which overcomes objections to prevzous correlations. It is shown that the tuyere diameter is only of small importance in determining the magnitude of the penetration. The data from operating furnaces correlate satisfactorily with the data from models whose cross section is a segment of a circle. A bubble-shaped gas space called a "raceway" normally exists in front of the nose of a blastfurnace tuyere. The periphery or "wall" of the raceway is well defined and is composed of densely packed charge particles. The blast. issuing as a jet from the tuyere, entrains gas from the raceway, in the usual manner of a jet, as it flows to the opposing wall. There it divides and flows back around the walls to be entrained once more. The blast must, of course, eventually leave the raceway and pass up through the charge column, but before it does it may, on the average, make several circuits of the kind described and in doing so it carries with it charge particles, which, because of their fast and circulating motion, suggested the name of "raceway". A fuller description of the raceway may be found elsewhere."' Here it is only necessary to mention, in addition, the measurement which characterizes its size. If an iron bar is pushed through the opened peepsight of a tuyere, .as far as it will go with ease, it will be stopped by the relatively impenetrable opposing raceway wall arid the distance that the bar has been pushed from the tuyere nose is called the "penetration". This measurement may be of practical importance and has; been the subject, with considerable success, of several attempts at correlation with other variables2-5 as stated in the next section. There is still, however, a serious objection to the most recent correlation,3 which is overcome by the correlation proposed in this paper. It will be shown that the objection is not trivial, in that the new correlation will attribute considerably different importance to the variables affecting the magnitude of the penetration. The data to be treated were made available by Wagstaff and are the same as those used in his correlation. They include measurements taken on small models, in which a cold air blast was used and no combustion occurred, and they also include data from operating blast furnaces at Wheeling and Fairless. The information from the blast furnaces will be shown to be in substantial agreement with those models whose plan views are segments of a circle and which are thus like segments of a blast furnace. First, Wagstaff's most recent correlation3 will be discussed and the objection will be given. Then the new correlation will be developed and its implications considered. CORRELATION OF J. B. WAGSTAFF Wagstaff's correlation is where and D — the penetration D,-the internal tuyere diameter V —the blast velocity in the tuyere

Jan 1, 1961

By James F. Watson, Jack L. Christian

The austenite to martensite solid state phase transformation in the 300 series austenitic stainless steels was studied over the temperature range of 788° to -423°F. The primary variables controlling this transformation are temperature, plastic strain, and chernical composition. Consequently, temperature effects were studied by measurements at 78", -100°, -320°, ad -423°F; plastic strain was controlled by cold-rolling the alloys varying amounts between 40 and 80 pet; and chemical compositions were varied by using 301, 302, 304 ELC, and 310 stainless steel alloys which exhibit varying degrees of austenite stability. The martensite contents of various alloys were correlated with several mechanical properties including yield and ultimate tensile strength, elongation, and notched tensile strength (Kt = 6.3). The yield and tensite strengths generally increased with increasing martensite content, but ) no correlation was observed between elongation and martensite content. The notched/un-notched ratio (Kt = 6.3) at -423°F exhibited a maximun at about 65 pct martensite. Attempts to correlate austenite stability (as measured by the Ms temperature) with both martensite content, and incremental increases in martensite content resulting from tensile testing were generally unsuccessful because the variable of cold Work could not be separated. As a result, only a general correlation of these variables was obtained. A (111) pole figure of austenite in a cold-rolled 301 stainless steel mas prepared an attempt to further investigate directionality as exhibited by mechan- ical properties. Yield strength was correlated with this pole figure, but ultimate and notched tensile strengths were not. 1 HE literature contains a wide variety of references pertaining to the austenite to martensite solid state phase transformation in austenitic stainless steel, see references 1 through 18. Discussions of the crystallography and kinetics of this transformation are given in references 2, 7, 8, 'and 11, while further discussions of austenite stability and hardening mechanisms are given in references 1, 3, and 10. Two important processing variables involved in this reaction are the degree of cold work and the temperature at which cold work is performed, and the nature of these effects are outlined in references 4 and 12, and 15 and 16 respectively. The latter two references deal primarily with cold rolling conducted at subzero temperatures. The effect of chemical composition on the austenite to martensite reaction was treated in detail by Eichelman and Hull, and they determined an equation for the M, temperature of this type of steel which included the effects of nickel, chromium, carbon, nitrogen, silicon, and manganese.5 Previous studies have shown that austenitic stainless steels of AISI types 301, 302, 304ELC, 310, and 301-N exhibit mechanical properties between 78" and -423"~ that are microstructure dependent, and the dependence of this microstructure on chemistry, temperature, tensile stress, and prior deformation is in general accord with previous investigations which have measured the effects of each of these variables on structure, or more specifically, the austenite-to-martensite transformation.lg The behavior of fully stable alloys, such as ATST type 310, at cryogenic temperatures is

Jan 1, 1962

By R. A. Nadler and

Specimens of Ti-155A (Ti-5Al-1.3Fe-1.3Cr-1.2Mo), Ti-6Al-4V and Ti-4Al-3Mo-1V were hydrogenated, aged to high strength levels, and subjected to notched stress-rupture tests and tensile tests at two strain rates. Both Ti-6Al-4V and Ti-155A were relatively unaffected by hydrogen in amounts exceeding those found in commercially -produced material. Inconsistencies in the data and a relatively low initial level of ductility prevented an accurate determination of the hydrogen tolerance for aged Ti-4Al-3Mo-1V, but there was no evidence that this alloy was any more susceptible to hydrogen embrittlement than Ti-155A and Ti-6A1-4V. THE metallurgical literature has been considerably enriched in the past five years by the publication of the results of many investigations which were concerned with the effects of hydrogen on titanium and its alloys. Although it is not the authors' intention to provide a complete literature survey of this vast field, it is worthwhile to summarize briefly some of the important factors which influence the embrittling phenomenon in a - B alloys. Some of the influencing factors are those of strain rate, temperature, and composition. Hydrogen embrittlement in a - B titanium alloys is now believed to be a strain-induced phenomenon, and whether or not embrittlement occurs at high hydrogen levels depends largely upon whether sufficient time is available for hydride precipitation. This condition is fulfilled by tensile testing at very slow strain rates or by rupture testing smooth or, preferably, notched specimens over relatively long periods. Conveniently, maximum embrittlement occurs at or near room temperature. The presence B - stabilizing elements, in amounts sufficiently small to prevent an all -B or nearly all -P condition, promotes hydrogen embrittlement and this tendency is believed to be related to the amount of a - B interfacial area present. Aluminum, by increasing the solubility of hydrogen in A titanium, greatly reduces the danger of hydrogen embrittlement, while oxygen has been shown to have detrimental effects.' The preceding discussion is based on experimental work performed on annealed a - P alloys. This early work has shown that annealed Ti-6A1-4V and Ti-155A are relatively insensitive to the embrittling effects of hydrogen.' Although no work has been reported on annealed Ti-4A1-3Mo-lV, the alloy would be expected to exhibit somewhat the same insensitiv-ity as Ti-155A. In sharp contrast to the voluminous literature on annealed titanium alloys is the paucity of reported investigations on materials receiving commercial heat-treatment cycles. To date, the most notable contributions in this field have arisen from two separate investigations on Ti-3Mn-1Fe-1Cr-1V-lMo, the so-called 3Mn comple~. These investigations

Jan 1, 1961

By Richard M. Foose

Most of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of rooling granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (TP 1725, this volume page 460). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. Mining and Milling Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast-southwest direction along the strike of the slate cleavage and are about 200 ft. .wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, I-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with 10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935, and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5' slope and in some of them there was stop-ing. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about a-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus a-in. product moves to a storage silo by bucket

Jan 1, 1948

By Richard M. Foose

Most of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of rooling granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (TP 1725, this volume page 460). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. Mining and Milling Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast-southwest direction along the strike of the slate cleavage and are about 200 ft. .wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, I-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with 10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935, and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5' slope and in some of them there was stop-ing. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about a-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus a-in. product moves to a storage silo by bucket

Jan 1, 1948

By Y. L. Yao

THE NaT1-type compound may be considered as the penetration of two diamond lattices in such a way that a superstructure of the bcc lattice is formed. Examples of the NaT1-type compound of lithium are LiZn, LiCd, LiA1, LiIn, and LiGa. Except for LiZn and LiCd, each molecule of these equiatomic compounds contains a total of four valence electrons. In LiZn and LiCd it was suspected (for example, see Ref. 1) that the fourth electron was withdrawn from the 18-shell of zinc or cadmium. An incomplete 18-shell would have to show strong paramagnetism. In 1955 Klemm and Fricke2 determined the magnetic susceptibility of LiZn, LiCd, LiA1, and LiIn (also NaTl and NaIn). The molar susceptibility of the outer electrons of LiZn and LiCd was found to be not strongly but weakly positive; that of LiAl and LiIn not negative but weakly positive. Thus they questioned the hypothesis about LiZn and LiCd in particular and the description of the NaT1-type structure in general. However, they did not determine the magnetic susceptibility of LiGa. This note is to report results for all five compounds of lithium. The starting materials are 99.9 pct pure lithium sticks containing less than 0.005 pct Na. 99.9 pct Zn, 99.9 pct Cd, 99.99 pct Al, 99.999 pct In, and 99.999 pct Ga. Weighed amounts of two components were wrapped in tantalum foil and placed in a graphite crucible. It was found that the tantalum sheath minimized the vaporization losses of lithium during melting. The sheath was easily stripped from the alloy rod and the tantalum in the alloy was barely detectable (less than 0.01 wt pct). The melting was performed in a resistance furnace under an argon atmosphere. Alloy specimens were annealed for 1 hr at 400°C in vacuum. The magnetic susceptibility at room temperature was determined by the Faraday Method, using the procedures previously described.' The results are shown in Table I. The interpolated values at 50 at. pct of Li and the average values at 48 to 52 at. pct of Li at 20°C determined by Klemm and Fricke2 are also shown. It is seen that the present value for LiZn and LiCd is slightly more positive but the present value for LiAl and LiIn is slightly less positive than their corresponding values. Also, it is noted there is an abrupt decrease of susceptibility of LiAl from 51.2 to 52.5 at. pct of Li. Klemm and Fricke2 found that the total susceptibility of LiZn, LiCd, LiA1, and LiIn is almost independent of temperature. slater4 gave a working expression for the diamagnetism of the atomic core as follows:

Jan 1, 1964

By Robert B. Fulton

The objective of this chapter is to discuss the interrelationship between industrial minerals and chemical manufacturing. It is intended to supplement rather than duplicate the commodity chapters. Particular emphasis is given to the pertinent chemical element and to market factors. Condensing this broad subject into a few pages of this handbook permits treating only the most important elements derived from industrial minerals. Hydrocarbons, which quantitatively dominate as raw materials for the chemical industry, are omitted, as are the metallic elements and the minerals covered in other "use" chapters such as phosphorous, potassium and nitrogen for fertilizers, and titanium dioxide for pigments. The remaining six elements of major importance are: boron, bromine, chlorine, fluorine, sodium, and sulfur. These elements are treated individually under separate headings. Table I (Jones, 1973) affords an overview of the main industrial minerals, the chemical products derived from them, and end uses of the products. Salt brines have particular importance as raw material sources for the chemical industry. Table 2 (Anon., 1967) is a chart of the chemical compounds derived from four types of brines: (1) Owens Lake-type brines, which are sources of boron and sodium compounds; (2) Midland-type brines, from which bromine, iodine, and chlorides of calcium, magnesium, potassium and sodium are derived; (3) Searles Lake-type brines, yielding boron, bromine, lithium, magnesium, potassium, and sodium compounds; and (4) Silver Peak-type brines, produced mainly for lithium. Market Attributes Some of the important market traits common to industrial minerals used by the chemical industry are listed below. 1. They are international commodities, such as fluorspar and sulfur, which largely move to foreign consumers. 2. Grade, and freedom from deleterious elements are important factors affecting their usability in chemical processes. An example is salt (NaCl) used in electrolysis where ultrapure evaporated salt is required to meet rigid specifications. 3. Purified products take on the characteristics of specialty items and command a distinctly higher price than the basic commodity from which they are derived. 4. In practically all cases, chemical users require some sort of cleaning or beneficiation of the naturally-occurring mineral to bring it to specification, and individual specifications may vary from user to user for essentially the same use. 5. In some instances it is necessary to strike a balance between what the vendor can supply and what the buyer requires, with the result that specifications have to be eased to afford the needed materials in marginal cases. 6. Because they tend to be bulk commodities, low cost for handling and transportation are important and such costs may limit the area from which a chemical user can draw his supply. For example, fluorspar from China and Thailand normally goes to Japan, while South African fluorspar can go either to Japan or to the US. 7. Shipments are usually in bulk and frequently in multiple-car, full-trainload or full-shipload lots to reduce transport costs, which in turn may require large terminal investment facilities.

Jan 1, 1983

By Richard M. Foose

MOST of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of roofing granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (Mining Technology, March 1944). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. MINING AND MILLING Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast southwest direction along the strike of the slate cleavage and are about 200 ft. wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, 1-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935 and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5º slope and in some of them there was stoping. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about 2-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus 2-in. product moves to a storage silo by bucket

Jan 1, 1945

By J. H. Wernick, S. Geller

A number of new AB, compounds, in which A is a rare earth or yttrium atom and B is Al, Mn, Fe, Co, or Ni, having the cubic MgCu, structure (Laves phase) are reported. In most of the compounds, the interatomic distances are normal; the lanthanide contraction is observed. However, in the compounds CeB2, B = Fe, Co, Ni, Ce appears to have a valence substantially greater than three; in CeAl2, Ce appears to be trivalent. These results are interpreted as vesulting from an energetically more favorable situation for the 4f electron of Ce to be lost to the 3d band of Fe, Co, nnd Ni. Evidence for the existence of homogeneitj! ranges in these compounds is presented. THE purpose of this paper is to report on the crys-tallographic investigations of a large number of new compounds, Table I, with the MgCuz structure (cubic Laves phase). It is a part of a continuing study of the magnetic properties and structures of binary systems involving the rare earths. In a previous paper' some of the magnetic properties of such systems were reported briefly. We have also reported2 a number of compounds of the CusCa type. The compounds were prepared by induction melting in Argon atmosphere of mixtures of stoichiomet-ric amounts of the constituent elements.* For most of the compounds fused alumina or silica crucibles were used as the containing vessel; graphite crucibles were used to prepare CeA12, NdAl2 and TbA12. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis-type Norelco cameras of 114.6 mm diam. The compounds AB2 belong to space group Fd3m-Ol with 8A in a): (000; 01/2 '/2;3) + 000-; b % XA and 16B in dl: (000; oVa %; 3) + 5/87; % %; 7e % Vs\£>. Because the intensities of the reflections on the powder photographs of the different compounds are similar, relative intensities were computed only for DyMnz for CrKa radiation, Table 11. In the calculation of intensities, the Thomas and umeda3 atomic scattering factors, corrected for dispersion,4 were used. The agreement between observed and calculated intensities leaves little doubt that DyMnz has the MgCuz structure. Crystallographic data for the ABz compounds are given in Table JII. Twelve of these compounds have been reported by other authors. A comparison of the published results with our work is given in Table W.* ers of elements of lower purity, to peritectic reactions in some cases, and to the presence of homogeneity ranges in these alloys, so that melting losses would still result in single phase alloys. The possibility of existence of homogeneity ranges in these compounds was investigated systematically only for GdMnz. At room temperature, the solid solution range is between

Jan 1, 1961

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600' to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k'?, where k' is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook' and by McAdams and Geil.' The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton' indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By R. F. Ashton, D. S. Thompson

In reporting results of precipitation hardening experiments, it is customary to include such conditions as solution heat-treatment temperature, specimen size, and quench medium as well as the aging time and temperature. One portion of thermal history that is often overlooked is the effect of the heating rate employed to achieve the aging temperature. It is the intent of this note to demonstrate the importance of the rate of heating to aging temperatures. This work was carried out on the aluminum alloy 7075 aged at 162oC, a temperature commonly used to obtain stress corrosion resistant tempers. A 2 in. thick plate of 7075 was quenched into 24°C water after solution heat-treatment for 2 hr at 470°C. Approximately 13 in. around the periphery of the plate was discarded to minimize quench rate variations, and the remainder was divided into 0.5 by 1.8 by 2.0 in. blocks which were held at room temperature, 24oC, for 4 days. This aging, or incubation period, at room temperature allowed a copious supply of GP-zones to form. Blocks were then heated at various rates to 162oC using the practices shown in Table I. Both single- and two-step aging practices were employed for each heating rate. The single step consisted of heating directly to temperature at the indicated rate while the two-stage practice included an interruption of heating for 7 hr at 107°C. In the case of the two-stage 100°C per min heating rate experiment, the specimens were returned to room temperature after 7 hr at 107°C where they were held for 16 hr be-fore finally heating at this rate to 162°C. This devia-tion in practice is not considered to be significant. Blocks were removed after various times at 162oC, and aging curves were determined from duplicate R. F. ASHTON and D. S. THOMPSON,Member AIME, are Senior Scientists, Metallurgical Research Division, Reynolds Metals Company, Richmond. Va. Manuscript submitted December 2. 1968. IMD Table I. Aging Practices Two-step Single-Step Heating Rate* Aging Aging Heating Method oC per Min A B Programmed Air Oven 0.23 * 0.01 C D Programmed Air Oven 0.93 ? 0.03 E F Air Oven at Temp -10 G H Oil Bath at Temp ˜100 *Heating rate was measured with a thermocouple at the center of a specimen. An average value between the starting temperature and 3°C below the aging temperature is reported for practices E-H. PRACTICES 70 — A B C E and G 50 - 2 4 6 810 20 40 60 HRS.AT 162°C Fig. 1—The influence of processing variables on 7075 aging curves. Fig. 2—7075 aged according to practice H (single-step aged, fast heating rate) for 3 hr. Magnification 100,000 times.

Jan 1, 1970

By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965

By E. V. Potter, H. C. Lukens

In general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation1 the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. Apparatus The apparatus used in these investigations is essentially the same as that used in the manganese work1 and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in gas volume are measured by volume gauge C which is essentially another mercury manometer in which the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 60 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. Method The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient tirne intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1949

By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By Dorsey Hager

North Central Texas has recently become a center of interest for the oil men of America. The bringing in of the McClosky well at Ranger, Eastland County, and the shallow pool at Brownwood, Brown County, in 1917, has stimulated interest in this area to fever pitch. Oil men from all over the United States are now investing there. The area of present interest is shown by the accompanying map (Fig. 1). The money spent in leases runs into millions of dollars. It is no exaggeration to say that a strip of country 200 miles (321 km.) long and 125 miles (201 km.) wide, comprising some 15,000,000 acres (6,070,310 ha.), has been leased practically solid at a cost for rentals and bonuses of at least $1 per acre. The test holes contracted for will certainly number 400, at a cost of at least $5,000,000. From what has been done in the past six months, $20,000,000 at least will be spent. To pay returns on this amount of money, new production to the extent of at least 12,000,000 bbl. must be obtained. At present, the production from new fields will not average over 5000 bbl. per day; three wells at Ranger are producing 3000 bbl.; 250 wells at Brownwood produce 1000 bbl.; and the Gray well, Coleman County, is as yet an unknown factor. However, at Ranger there is every indication of developing a good pool covering from 1500 to 2000 acres (607 to 809 ha.), more or less, but the wells are deep, 3400 to 3800 ft. (1036 to 1158 m.), and cost $35,000 to $40,000 to drill. Large wells are necessary to pay for such expensive holes. As new wells are drilled, the gas pressure will be lowered rapidly, and large production need not be expected. For those oil men who expect a second Cushing or an Eldorado, Ranger holds little of promise. At Brownwood, Brown County, there are some 250 shallow wells (depths from 200 to 350 ft.) averaging 4 to 7 bbl. per day. There is a chance of an extensive producing area for these shallow sands to the southwest, and the opening of several thousand acres of shallow oil territory, and also some promise of deeper oil horizons in the Ranger horizon, but probably all under 2500 ft. At present, the lease brokers and speculators, and only a handful of oil men, have made any money. More fields must be developed, and it is more particularly with these possibilities that this paper deals. Lack of water for drilling purposes has undoubtedly held back development so far this year; this part of Texas has had a drouth for two years and there is an actual scarcity of water. Geological investigations so far undertaken cover nearly all the area outlined, and while pakt of the

Jan 1, 1920

I. PRESIDING OFFICER, At all business meetings of the Institute the President, or, in his absence, the First Vice-President, or, in the absence of both of them, any other Vice-President or Director, chosen by the meeting, shall preside. At all other meetings of the Institute the President, or, in his absence, one of the Vice-presidents shall preside. If none of these be present the meeting shall elect a Chairman. The President shall do and perform such other duties as may from time to time be assigned to him by resolution of the Board of Directors of the Institute. II. ORDER OF BUSINESS. At each business meeting of the Institute the order of business shall be as follows: 1. Reading of minutes of preceding meeting. 2. Report of the President, 3. Report of the Treasurer. 4. Report of the Secretary. 5. Election of Directors. 6, Reports of Standing Committees. 7. Reports of Special Committees. 8. Special Orders. 9. Miscellaneous business. This order of business may be changed at any meeting, by a vote of a majority of the Members and Associates present. At all sessions of the Institute, other than business meetings, the order of proceedings and the time of adjournment shall rest in the discretion of the presiding officer. III. SECRETARY OF THE INSTITUTE. The Secretary shall keep a record of the proceedings of all the meetings of the Institute, He shall be custodian of the corporate seal, of the minute books and of all the legal documents belonging to the Institute. He shall have charge on behalf of the Institute of all correspondence. He shall notify all Officers and Directors and all members of committees of their election and appointment; shall issue notices of all meetings of the Board, and of the annual and other business meetings of the Institute; and shall, in calling special meetings of the Directors, specify the objects of such meetings. He shall act as clerk at all the meetings of the Board of Directors and at all meetings of the Institute, The Secretary shall be custodian of all technical or scientific papers submitted to the Institute for its consideration and shall have general charge and supervision of the editing and proof-reading of all material published by the Institute, and of the distribution thereof. The Secretary shall be the custodian of all back numbers of the Transactions and other publications of the Institute. There shall be kept under his direction an account in ledger form of all such back numbers, He shall on the first day of January of each year submit to the Library Committee a statement of the number of copies of Transactions, magazines and other publications printed during the preceding year, giving the number distributed and remaining undistributed; also a statement covering additions to and withdrawals from the total stock of Institute publications, with the number 'remaining on hand at date of statement,

Jan 1, 1928

By A. W. D. Hills

This paper describes the development of a generalized integral-Wofile method for the analysis of heat transfer dwing solidification. The method is extremely flexible, and can be applied to a wide range of situations. This flexibility has been achieved by characterizing the solid metal layer in terms of two parameters, and by developing two simultaneous nonlinear differential equations for these parameters in terms of the heat fluxes crossing the boundaries of the solid layer. The use of these equations is illustrated in a series of examples which involve the solidification of pure metals at zero superheat cooling under different conditions. The simplicity with which the method can be extended to treat more complicated jwoblems is illustrated in a further example which involves natwal convection effects in the liquid metal. ThE rate at which molten metal solidifies in an industrial casting process, and the structure of the cast product, are both controlled by the rate at which heat can be removed from the casting. A knowledge of heat transfer rates is thus essential to the control of the process and to the control of the structure and soundness of the final casting. Heat transfer rates during real solidification processes cannot be predicted by formal mathematical techniques, however, because nonlinear boundary conditions are involved. Approximate methods are normally used, and these have included electrical and hydraulic analogue techniques, finite difference methods, and the integral-profile method. Considerable effort has been devoted to the development of the first two techniques, but the integral-profile method has been used very little so far. This is unfortunate because the method is capable of providing relatively accurate solutions for the heat transfer equation during solidification without involving large amounts of computer time. A further advantage of the method is its flexibility, although this is not apparent from the integral-profile solutions that have been developed to date. These solutions have been derived for the solidification of molten metal at zero super-heat under cooling conditions involving either a constant heat flux from the cooled surface;' a constant heat transfer coefficient at the surface,'-3 or a specified variation in the surface temperature.4,5 A generalized integral-profile method is presented in this paper which can be used to predict unidirectional solidification rates under a very wide range of more realistic cooling conditions. The use of the method is illustrated in a series of problems involving pure metals, or skin forming alloys, solidifying at zero super-heat. However, the principal advantage that this method has over the previous integral-profile methods is the ease with which it can be extended to treat more complicated solidification problems. This is illustrated by considering a problem in which super-heat is liberated from the liquid metal by natural convection during the solidification process. In the final section of the paper the generalized method is compared with previous methods used to predict solidification rates and its extension to more complicated solidification problems is briefly discussed.

Jan 1, 1970

By A. J. Phillips, A. A. Smith, J. S. Smart

THE preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in properties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. PREPARATION OF HIGH-PURITY COPPER The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuS04-H2SO4 electrolyte using bagged anodes, low current .density (5 amp. per sq. ft.) and low temperature (25°C. max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe 2(S04)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then refiltered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2S04 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 434 by 43a by I-in anodes cast from high-quality electrolytic wire bar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars-which would result in fouling of the contacts and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941