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By Robert B. Fulton

Commercially, celestite (SrSO4) is the predominant strontium mineral. Among other strontium-bearing minerals, only strontianite (SrCO3) occurs commonly; however, it is rarely an item of commerce. Production of celestite is principally in Mexico, Spain, and Turkey. An attempt to produce celestite in Canada was unsuccessful. The United States, which is wholly dependent on imports, chiefly from Mexico (99%), is the largest consumer of strontium. Lesser quantities are consumed in Japan and Europe. The Federal Republic of Germany is the principal source of strontium compounds imported to the US. Uses The principal uses of strontium are for the manufacture of strontium carbonate and nitrate. Carbonate is used in glass for TV tube face plates and in ceramic ferrites for magnets. Nitrate is used in pyrotechnics, mainly in safety flares, to which it imparts a characteristic brilliant red color. Minor amounts of strontium compounds are used in electrolytic zinc manufacturing where the carbonate is used to remove unwanted lead. Small quantities are consumed in greases, ceramics, soaps, alloys, and pharmaceuticals. Specifications Typical celestite specifications for the carbonate and nitrate markets are shown in Table 1. Specifications of manufactured carbonate, sold in two grades, one to the glass industry and the other for ceramic ferrites, are shown in Table 2. Both grades of carbonate are shipped in palletized 50-lb bags. Glass grade material is shipped in bulk by rail. [ ] Manufacturing Processes The following description is adapted from Anon. (1980) . The manufacturing process for strontium carbonate and strontium nitrate chemicals is conceptually simple. Strontium nitrate is made from strontium carbonate in two additional steps. The production process begins with celestite, the natural form of strontium sulfate. In the first step the ore is crushed, ground, and mixed with coke. This mixture is then fed into a kiln where the ore is reduced at high temperatures to strontium sulfide; the coke is added to the ore as a source of energy and carbon. The carbon combines with the oxygen [ ]

Jan 1, 1983

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett' reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y', respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By M. Bevis, E. O. Fearon, P. C. Rowlands

Fe-Ni and Fe-Ni-C martensite specimens have been deformed in compression at room temperature and the habit planes of operative deformation twins determined by two-surface optical trace analysis. The full orientations of the martensite crystals were determined from divergent X-ray beam diffraction patterns. The experimental results are in excelled agreement with predicted twinning modes. In particular, the habit planes of some deformation twins in bcc martensites are consistent with a "Type XI compound'' twinning mode with Kl, Kz, 71, 77~ elements given by {5, 8, 11) {ioi}, (33) (ill) Tetragonal derivatives of this mode are operative in bct martensites. UnUSUAL deformation twinning modes have been reported by Richman' to occur in Fe-Ni-C martensites with bcc and bct structures. The twin habit planes were determined by single-surface trace analysis (pole locus method) and the remaining twinning elements were determined from the geometry of twin-twin intersections. The indices assigned to the observed habit planes are (3 101, "(089)" and "{0, 1,13)" or "{1,2,7} ", and only in the first case do the twinning elements correspond to a predicted twinning mode. This is mode 1.4 in the paper by Bevis et al. The results presented in Ref. 2 indicate that previously unpublished bcc and bct modes should be operative in preference to the (130) mode and anomalous modes reported by Richman. In view of these results and the uncertainties involved in determining habit planes from single-surface trace analysis and twinning elements from twin-twin intersections5 a two-surface trace analysis of deformation twins in Fe-Ni and Fe-Ni-C martensites has been carried out. EXPERIMENTAL PROCEDURES Two alloys with compositions Fe-23 pct Ni-0.6 pct C and Fe-30.4 pct Ni were prepared from 4N pure materials by induction melting under a vacuum of 10"5 mm Hg. The alloys were homogenized at 1350'~ for 5 days. Both of these alloys are austenitic at room temperature with M, temperature - — 50"C. The aus-tenite grain size of the Fe-Ni-C alloy was approximately 300 to 400 p. The Fe-Ni alloy was remelted in a vertical tube furnace and the melt lowered slowly from the hot zone of the furnace to produce s ingle -crystal austenite specimens. Specimens approximately 10 by 5 by 5 mm were cut from the ingots and quenched to various temperatures below the Ms temperature. The specimens were elec-tropolished in a 10 pct perchloric acetic electrolyte before being deformed in compression at room temperature. Martensite plates which exhibited profuse deformation twinning were selected for analysis and the specimen polished on a second surface such that the two surfaces which contained the martensite plate enclosed an obtuse angle of approximately 145 deg. The specimens were then electropolished to reveal the traces of the deformation twins on both surfaces. The full orientations of the martensite crystals were determined using a divergent X-ray beam technique (Kossel line technique) employing an AEI SEM2 electron probe microanalyzer. Details of this technique which include a detailed description of the Kossel camera attachment to the microanalyzer used in the present experiments have been discussed elsewhere.3 Only additional details relevant to this investigation are discussed here. The specimens were mounted with one surface normal to the incident electron beam as illustrated schematically in Fig. 1. The martensite plates to be analyzed were located using the normal scanning equipment of the microanalyzer. The position of the electron beam and hence the position of the source of divergent X-rays generated within the crystal could be located to within 1 p. Exposure times of approximately 8 to 10 min were required for back-reflection Kossel patterns and it was found that useful diffraction patterns could be obtained consistently from heavily deformed martensite plates. A reference line (carbon contamination mark) produced on the two surfaces of the specimen by scanning the electron beam in a direction having a known relationship with the reference !ine in the X-ray camera enabled the full orientation of the crystals to be determined. Martensite plates with widths as small as 8 p could be oriented using this procedure. The Kossel line patterns were interpreted using the charts developed by Rowlands and ~evis~ as generally

Jan 1, 1969

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By RAY J. CORFIELD

IN a previous paper, "Electric Shovel Operation at Utah Copper Mine," which was read before the Western Division of the American Mining Congress, the problem of electrifying a fleet of steam shovels was described. This paper deals with the electrification of the haulage system which, when completed, will make the mining operation completely electric, with the exception of drilling operations which will continue to be performed by air. The general layout of the haulage system involves the use of heavy curves in addition to heavy grades of between 4 and 5 per cent. In a mining operation of this kind no trackage can be called permanent; this complicates the overhead construction somewhat and makes it necessary to design special forms of trolley construction, some of which will be described in detail below.

Jan 1, 1929

By J. P. Hirth, A. H. Clauer

A simple graphical method is presented for the determination of climb forces on dislocations exerted by uniaxial stresses. In conjunction with standard stereographic projections, the technique is applicable for any crystal system. Climb forces on glide dislocations in bcc crystals are determined as an application. In connection with a study1 of elevated temperature creep of molybdenum single crystals, a detailed analysis of the climb force on a dislocation was necessary. In general, such forces can be calculated for an arbitrary dislocation segment from the Peach-Koehler equation2 (or one of its variants3"6) where Fk are the components of the force per unit length of dislocation line, ?i of the unit sense vector tangent to the line, ojl of the stress tensor, bl of the dislocation Burgers vector, and is the Einstein permutation operator with components ?123 = ?231 = ?321 = —?132 = — ?321 = —?—213 = unity, and all other components zero. It is understood in the suffix notation of Eq. [I.] that repeated indices are to be summed over 1, 2, and 3. For the most general coordinate system, the matrix manipulations required to solve Eq. [I] are fairly complex. However, a simplification can be achieved by specifying a coordinate system based on the dislocation in question. The pertinent system involves cartesian coordinates xi, x;, xi, with attendant unit vectors e'i; ei being parallel to the Burgers vector b, and e'3; being parallel to the climb directions (b x ?), i.e., normal to the slip plane. In this coordnate system b = (bi, 0, 0) and ? = (?'1,?'2, 0). Hence, Eq. [I] yields for the climb force per unit length F3 = ?'2s'11b'1—?'1s'12b'1 [2] The first term on the right side of Eq. [2] is the climb force on the edge component of the dislocation, while the second is the (cross-slip) force normal to the glide plane acting on the screw component. Thus, the problem of determining the climb force reduces to that of resolving the stress components —il and s'12 in the xi coordinate system. Several authors7- l0 have shown, for the glide case, that such stress resolution can be performed most readily by graphical methods. Therefore, we present a similar method for the climb case. Of the suggested methods, we follow that of Hartley and Hirth,9 which can be performed directly with a standard stereographic projection for the crystal system in question. We treat the case of simple tension, or compression, this being the most common creep test in which climb is important. A set of cartesian coordinates (x1, x2, x3) is fixed with x3 parallel to the specimen axis. This set is connected to the x'i set by the factors defined in Table I. A perspective view of the coordinate systems relating them to the glide ellipse, is given in Fig. 1, while a stereographic projection of the coordinate systems is presented in Fig. 2. The transformation matrix connecting the xi and xi coordinates is x'i =aijXj [3] where an a11 a13 aij = a21 a22 a23 a31 a23 [4] s The corresponding transformation for the stresses is i [5] The only nonzero component of okl for the simple tension case is s33,. Hence, using Eqs. [4] and 151, we find that Eq. [2] becomes F3 = b'1s33 sin2 cos ?[cos ? sin a - sin ? cos a] [6] = m1b'1s033 sin a- rn2b's33 cos a where sin a = 5: and cos a = ?i, with a the angle measured from b to ?, i.e., a polar angle in the x1, x2 plane. The same equation with a sign change applies for compression. A graphical plot of the "Schmid" factor m1, relating to the climb force on the edge component, is presented in the stereographic projection of Fig. 3. In this projection the glide plane normal points toward the top of the page and the glide direction points normal to the plane of the page. To use the graph, one

Jan 1, 1970

By Peter L. Langsjoen, Kenneth L. Maloney

Ten small and intermediate-sized (4.5 Mg/hr to 113 Mg/hr steam--10,000 to 250,000 lb per hr) coal-fired boilers in the upper Midwest have each been tested on both a bituminous eastern coal and a subbituminous western coal. The purpose of this study was to determine the feasibility of substituting western subbituminous coal for eastern bituminous coal as a means of reducing the SO, emissions from this class of boiler and to demonstrate the feasibility of greatly expanded western coal utilization as a means of reducing the use of oil and gas. The scope of this study was such that the representative boiler types were tested on both eastern and western coal for a period of time sufficient to completely characterize their individual emission and operational characteristics.

Jan 1, 1978

By Leon Nelson

SEVERAL factors which affect the segregation and solidification of killed hot-topped steel ingots are: (1) pouring temperature, (2) volume in the hot top, (3) taper in the ingot, (4) pouring rate by varying the nozzle size, (5) segregation of several elements, (6) moving ingots before completely solidified. In most of this discussion, segregation will be measured in terms of carbon variation only. All the data given are results on S.A.E. 1040 analysis of fully killed steel direct-poured in hot-topped molds giving 20-in. square ingots. Thus the variables of analysis and ingot size and contour are eliminated. Segregation results are all on the rolled-bloom size, not on the ingot itself. They are results from plant-control work and not results of special research on ingot segregation.

Jan 1, 1937

By T. F. Witherbee

In the sections, Figures 1, 2, and 3, are shown three crucibles that have been applied to substantially the same furnace, all the conditions having been the same except a variation of one foot of bosh, and a slight variation in the angle of the same. The bosh of No. 3 was originally the same as No. 2, the additional foot in diameter being the result of three months' cutting. Beginning with No. 1, which mas 5 feet 6 inches diameter, with tuyeres 5 feet 4 inches high, and cinder-tap four feet from bottom, great trouble was found in holding iron a proper length of time, four hours being the outside limit when working well, and two hours or less if working badly. "Break-outs" through the iron

Jan 1, 1880

Mar. 3-7, ASTM, spring meeting and commitee week, Hotel Statler, Cleveland. Mar. 4, AIME, Morenci Sub-Section, Longfellow Inn, Morenci, Ariz. Mar. 5, AIME, Chicago Section, Ladies Night, Chicago. Mar. 10-13, National Electrical Mfrs. Assn., spring meeting, Chicago. Mar. 10-14, National Assn. of Corrosion En-Engineers, annual convention, Galveston. Mar. 11, Society for Applied Spectroscopy, 6 pm, supper, Tosca's; S pro, meeting, Socony-Vacuum Training Center, 63 Park Row, New York. Mar. 16-19, American Institute of. Chemical Engineers, Atlanta Biltmore Hotel, Atlanta. 'Mar. 17-21, ASTE, annual meeting, Chicago. Mar. 20, AIME, Philadelphia Section, Engineering Bldg., University of Pennsylvania, Philadelphia. Mar. 22-Apr. 6, Chicago International Trade Fair, Navy Pier, Chicago. Apr. 1, Society for Applied Spectroscopy, Socony-Vacuum Training Center, 63 Park Row, New York.

Jan 1, 1952

By T. F. Witherbee

IN the sections, Figures 1, 2, and 3, are shown three crucibles that have been applied to substantially the same furnace, all the conditions having been the same except a variation of one foot of bosh, and a slight variation in the angle of the same. The bosh of No. 3 was originally the same as No. 2, the additional foot in diameter being the result of three months' cutting. Beginning with No. 1, which was 5 feet 6 inches diameter, with tuyeres 5 feet 4 inches high, and cinder-tap four feet from bottom, great trouble was found in holding iron a proper length of time, four hours being the outside limit when working well, and two hours or less if working badly. "Break-outs" through the iron

Jan 1, 1880

By Lawrence Adler

The authors are to be complimented on using a novel and potentially helpful technique to analyze the effects of mine roof trusses. However, some criticisms of their application and analysis seem appropriate to further its acceptance. This discussion will deal with the normal structural analysis format covering: 1) material. 2) load, 3) structure, and 4) analysis. It will then briefly review the testing procedures and finally cover miscellaneous items. That the analytical and testing results admittedly disagreed by several orders of magnitude, indicates a need for improved understanding. The introduction of data determined previously was not assisted by references to "Interim" or "Preliminary" reports. This material should have been concisely reformulated for the open discussions that Transactions encourage. In addition, many important simplifying assumptions are tacitly made without recognition, and much less, an attempted justification.

Jan 1, 1979

A meeting of the Board of Directors was held in the Council Room of the U. S. Bureau of Mines, Interior Building, Washington, D. C., on Friday, June 21, 1918, at 4 p. m. Twelve members of the Board, the Secretary of the Institute, and nine guests were present. Upon the petition of 28 members of the Institute residing in or near Washington, D. C., a Washington Section was authorized. A committee was appointed to nominate officers and prepare a set of by-laws. The report of the Treasurer was presented in writing, accepted, and ordered filed. Thirty-nine members, 12 associates and 8 junior associates were elected. Two members were reinstated. One resignation was accepted. The dues of 64 members were suspended on account of their being on active war duty.

Jan 8, 1918

By F. G. Tickell, R. C. McCurdy, O. E. Mechem

The behavior of fluids in the voids of a rock is fundamental to the study of many of the problems of oil-field development and production. For it is by virtue of these openings between grains that oil and gas are able to move through the rock, to be contained by the rock, and to pass from the rock into the well. The capacity to contain fluids is measured by the porosity of the rock, and the ease of fluid movement is governed by the permeability. When the engineer wishes to estimate the amounts of oil and gas in an underground reservoir he is often concerned with the porosities of the rocks and, when dealing with problems relating to rate of production, he is more likely to be interested in the permeabilities of the rocks. Rocks are permeable because they are porous, but they may be porous without being permeable. Clays are very porous, and yet they are impermeable from a practical standpoint. Attempts have been made1 to correlate permeability with porosity for certain rock members but, where a definite relationship between these two properties is found to hold, it is purely fortuitous and local. Porosity and permeability do not necessarily bear any quantitative relationship to one another. The porosity of a substance is the percentage of void volume to bulk volume. The petroleum engineer is usually interested only in the inter-granular voids that are accessible to fluids. In measuring porosity he does not wish to include scaled openings. The measurement he desires is one of "available porosity," otherwise called "apparent porosity." The porosity of a natural aggregate of solid grains, such as a sandstone or clay, is governed by: (1) Grain-size distribution, (2) angularity of grain, (3) colloidal content, (4) degree of compaction. It is not difficult, for unconsolidated rocks, to measure the effect of any one of these when it alone is varied, and then to predict what the effects on porosity will be for such single variables. It is very difficult, however, if not

Jan 1, 1933

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET's and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.' More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET's. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET's with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

THE developments in construction and operation of the basic open-hearth furnace that have taken place in recent years have placed new emphasis on the vital influence played by regulation and control of the combustion system in both furnace production and furnace life. The several factors influencing flame development, such as regulation of fuel supply, air supply, air preheat, furnace draft, and furnace reversal, must be controlled closely if successful furnace performance is to be accomplished. Rugged instrumentation of distinctive design is required to supply dependable information concerning operating conditions, which is requisite to proper regulation of combustion. This chapter attempts to give a practical discussion of the various features of open-hearth practice and instrumentation related to the efficient heating of the furnace, control of temperature, and protection of the furnace structure from accidental overheating. The appended references will be helpful to readers wanting a more detailed treatment of individual topics. OPEN-HEARTH FUELS The most important open-hearth fuels are listed in Table 4-1 together with their compositions and other data useful for combustion calculations. A detailed discussion of open-hearth fuels is not attempted here, but certain factors peculiar to their application to this type of process are briefly indicated on the following pages. Very often an open-hearth shop is forced by economic factors to use a fuel to which its furnaces are not very well adapted, because the general fuel-allocation scheme for the works as a whole seems to demand it. Often a variable marginal supply of coke-oven gas or tar must be consumed by the open hearth, together with another fuel such as producer gas, natural gas, or oil, to fill out total requirements. Most furnaces employ more than one kind of fuel during their usefu1 life; however, the partial redesign

Jan 1, 1951

By B. Ladanyi

The problem of rock behavior under concentrated loadings has been the subject of a number of studies in the past and has been receiving increasing attention by rock mechanics investigators in recent years. Its application covers various fields, but main interest in its solution has arisen in connection with the problems of drilling, bearing capacity, and rock testing. These widely different purposes and fields of interest probably have been one of the reasons why, in spite of the large amount of published experimental data and several theoretical studies, there are still many points which need further clarification. Another reason for this situation undoubtedly is due to the fact that the rock behavior in indentation is complicated by a great number of influencing factors. Experimental evidence shows that, depending on the rock type (mechanical properties, porosity), environment (ambient effective pressure, pore fluid, temperature), and the type of loading (indenter shape, initial embedment, load level, loading rate), the rock response to indentation may vary within very large limits. The widely different rock behavior has made it impossible up to now to treat the problem with a consistent single mathematical theory, but has required instead a series of simplified models covering only certain most important events in the failure sequence. As far as the theory of rock indentation is concerned, this chapter does not add much new information. Its main purpose is, however, to state the indentation problem in a general manner and to indicate which points need to be studied in more detail before its definite solution is attempted. Also, since excellent reviews of the state-of-art of rock indentation in drilling have recently been given,1-4 this will not be repeated here, and only references pertinent to the points of the problem under study will be quoted. The theoretical part of this study attempts to give a quantitative evalu-

Jan 1, 1972

By W. C. Weslow

AN extended program devoted to the development of a matrix for holding diamonds of a size and. kind not heretofore generally used is being carried on by the Carboloy Company, and this paper describes the part of the development that affects mining and its allied industries. Labora-tory and field work so far has indicated the following: 1. Tungsten carbide and cobalt form the most desirable known matrix material for the holding of diamonds for drilling work. 2. Industrial bort diamonds in sizes and of a class not generally heretofore acceptable and therefore less expensive can be successfully held in this cemented carbide matrix. 3. In exploratory drilling, the combination of bort diamonds, impreg-nated throughout a matrix of tungsten carbide and cobalt, when fabri-cated onto drilling crowns, is an indicated economic substitute for drilling crowns in which the diamonds are set by hand, mechanically or by casting. 4. This impregnated type of drilling crown or bit has definite possi-bilites of revolutionizing the drilling of blast holes, particularly in the harder formations. This will be brought about by the development of high-speed light-weight rotary equipment using an impregnated diamond bit to replace the percussion drill now in general use. (The development of this rotary equipment is well past the laboratory stage at this time.) 5. That the use of a rotary bit is a preventive measure in the fight against silicosis. The development of this product was started by G. F. Taylor at the Research Laboratories of the General Electric Co. It was early recog-nized that it had possibilities in the drilling field and the present product is the result of considerable experimental work with other powdered metals as well as with tungsten carbide and cobalt.

Jan 1, 1940