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By T. M. Kegley, J. H. Frye, D. L. McElroy, M. L. Picklesimer, E. E. Stansbury

Measurements of rate of growth, thermodymmic quantities, and partitioning of Mn are reported for high-purity eutectoid Fe-C and Fe-C-Mn steels for the auistenite-pearlite reaction. Evaluztion of the cotnstants of a derived-rate equation with these data indicate that Mn additions cause the decrease observed by increasivg the activation energy and apparent activation entropy or the movenment of complexes at the interface. A diffusion-controlled mechanism is not required. Appreciable partitioning of Mn to cementite occurs entirely behind the austenite-pearlite interface for more than 30°C of subcooling. ThE growth of pearlite from austenite has been extensively studied over a period of years. but the rate-controlling step in the process is not known nor is the mechanisrn of the effect of alloying elements understood. A comprehensive review of the subject has been given by Mehl and Hagel. The present study has been concerned with further considerations of the effects of alloying elements on the rate of growth of pearlite. Analytical relatioriships for the rate of growth of pearlite have been considered by Zener.2 Turnbull,3 Machlin,4 Cahn.5 Frye,6 and Frye et a1.7 The derived expressions in each case involve the free energy of the transformation. the interlamellar spacing. and some rate term of the nature of the diffusion coefficient. mobility or frequency of occurrence of some rate-determining step. The treatments. of course. differ in detail. Further consideration is given in the present paper to the equation of Frye, Stansbury. and McElroy which was derived from modified absolute rate theory without in any way specifying the mechanism of the reaction. This equation is r=c ? T ? F exp -?E*/RT [1] where r = rate of growth in mm/sec c = a constant AT = equilibrium transformation temperature minus actual transformation temperature "C ?F = free energy per mol of austenite minus that of pearlite ?E* = activation energy R= gas constant ?F in Eq. [1] is computed from the following: ?F=?H?T/To - ?T' dT' ?T' ?CdT"/T" [2] To To where AH is the enthalpy per mol of austenite minus that of pearlite at the equilibrium temperature, To, and AC is the difference in specific heat between austenite and pearlite per mol. Subsequently, Darken, Fisher, and Galligan8 have reported that a layer of ferrite separates pearlite from austenite at the growing interface (i,e., the advancing face of Fe3C is in contact with ferrite, not austenite) and the ratio of the thickness of this layer to the spacing of the pearlite has not been found to vary with alloy content or transformation temperature. This observation does not require any alteration in the above equation: however, it may require that a different significance be attached to the factor, AT. The AT term appears in Eq. [I] as a consequence of a factor for the amount of growth per complex transformed at the interface.* It is based *This is not the sole reason for expecting such a relationship. See Ref. 7._______________________________________________________ on a l/2 ?T dependence of the interlamellar spacing. Zener2 has developed a theory which leads to Soa 1/?V where So = the pearlite interlamellar spacing. This relation is as consistent with the data on interlamellar spacing as other relationships, although, as pointed out by Mehl and Hagel,1 the data are not sufficiently precise to consider the relationship as confirmed. The work of Darken, Fisher, and Galligan8 requires that the above be written where f = the thickness of ferrite layer between austenite and pearlite. The present paper is concerned with iron-carbon-manganese eutectoid alloys and reports experimental measurements of the following kinds: 1) the effect of

Jan 1, 1961

By H. P. Leighly, F. C. Perkins

THERE have been several statements in the literature about the difficulty of producing single crystals of high-purity (99.99pct) by the strain-anneal method. Consequently, investigators tend to employ low-purity aluminum for their single-crystal experiments, or else resort to the Bridgman or other techniques which depend on solidification for the production of single crystals. The following paragraphs describe a solid-state method for the manufacture of single crystals of high-purity aluminum which should provide crystals with greater perfection than those formed by solidification. The starting material for this method of producing single crystals was secured from the Aluminum Corp. of America and has a purity of 99.99 pct, the balance being trace amounts of impurities. Specimens approximately 1 by 4 in. are sheared from sheet having a nominal 0.050 in. thickness. The specimens are given a preliminary anneal at 640°C for approximately 3 hr in order to remove fabrication strains and to produce an average grain size of about 1/4-in. diam. The specimens are then etched in Tucker's etchant (45 pct HC1, 15 pct HNO3, 15 pct HF and 25 pct H2O) to remove the oxide film. Critical strain is applied by wrapping each specimen about a 1 3/4 in. round and subsequently straightening it against a flat surface. The high-purity aluminum sheet is sufficiently soft that this operation can be accomplished by ordinary finger pressure. The specimens are immediately annealed again at 640°C for 3 hr and reetched for examination. Ordinarily, considerable growth of certain of the grains will have occurred, and occasionally a single crystal will be produced on the first attempt. The procedure of alternately straining, annealing and etching is repeated until the majority of a batch of specimens contains usable crystal sizes. Typical examples are illustrated in Fig. 1. The greatest changes in crystal sizes are produced in the initial treatments. As the average crystal sizes get coarser in the later treatments, the sever- ity of the strain must be increased in order to produce grain boundary- migration. This increase in severity is effected by decreasing the diameter of the round used for straining (to 1 1/2 in., for example) and/or wrapping the specimens about the round twice, with opposite faces in contact with the round, before flattening. Usually the strain treatments described are not severe enough to produce nucleation in coarse grain high-purity aluminum. The growth of grains occurs by strain-induced grain-boundary migration. It has been observed that the grain boundaries move most readily during the first hour or so of each annealing treatment and that the rate of movement decreases with extended holding times at temperature. Prolonged annealing treatments are therefore not usually beneficial. Similarly, the rate of growth of each crystal appears to depend upon the orientation of the crystal with relation to those of its neighbors. Frequently island grains are formed after the initial heat treatment as the result of slow grain-boundary migration. These sometime become stationary during later heat treatments. Twin orientation interfaces are frequently developed during annealing. These imperfections can usually be removed by increasing the severity of strain to produce actual nucleation of new grains of more favorable orientation at the imperfection interfaces. The largest single crystals produced in our laboratory by the above method measured 4 by 1 by 0.050 in. Examination of Laue back-reflection patterns from a limited area of the specimens, gave no evidence of polygonization. Probably there is some indication of polygonization in the original grain area provided a more sensitive technique is used for detection. Experiments to produce wider specimens were less successful, possibly because wider sheets increase the complexity of the strains induced by deformation and promote widespread nucleation. Grain boundary migration occurs preferentially in a direction parallel to the longitudinal axis of the specimen. The choice of specimen geometry with respect to the rolling direction of the sheet appears to be immaterial in regard to the production of single crystals.

Jan 1, 1961

[59H1-Water Law and Its Significance to the Mining Industry by Wells A Hutchins 59H2-Relation of Land Subsidence to Groundwater Withdrawals in the Upper Gulf Coast Region, Texas by Leonard A Wood and A G Winslow 59F3-Hydraulic Mining of Gilsonite and Its Application to Coal Mining by J H Baker 59H4-Recovery of Phosphates by In Situ Fluid Mining by Sylvain J Pirson 59F5-Coal Cleaning Plant Design for Minimum Operating Labor by Wm M Bertholf and John D Price 59F6-Coke Combustibility A Neglected Characteristic by J D Price 59B7-Union Carbide's Uranium Operation at Maybell, Colorado by K W Lentz and F T Temple 59H8-A Rapid Method for Estimating Alumina in Feldspathic Sands by Hugh H Bein 59H9-Water Laws as Related to Dredging in Idaho by Robert A Lothrop, Richard B Porter, and Robert P Porter 58B19-Separation and Washing of Alumina Process Residue by Morton Handelman 59B11-Feed Preparation and Froth Modification for Fatty Acid Flotation by Carl C Martin and Burt C Mariacher 59B12-Design Requirements for Tailing Disposal in the Southwest by E Vern Given 59B13-Semi-Dome Shaped Buildings for Bulk Storage by Edward E Ives and William L Payne]

Jan 1, 1961

By D. W. Lillie

Property changes produced by irradiation of Al-0.4 wt pet Li alloys at 270°C to a burnup of 0.155 pct of all atoms are described. Metallographic evidence of the formation of internal pores and the concentration of gases at grain boundaries is shown. Some conclusions are drawn concerning desirable property characteristics for resistance to radiation swelling. RADIATION induced gases are of great practical significance in nuclear engineering since they affect the behavior of fissionable fuels and control rod materials. In fuels the gases xenon and krypton are the major offenders, producing serious em-brittlement at low irradiation temperatures and gross swelling at high irradiation temperatures. In control rod materials containing boron, the production of helium from the B 10 (n, 0) Li7 reaction produces similar reactions. Since the trend in reactor design is for operation at increasingly high temperatures, the phenomenon of high-temperature swelling by these induced gases has been the subject of considerable recent study. The objectives of such work have been to obtain engineering information and quantitative data on the effects in specific fuels and control rods and to obtain further understanding of the mechanism of gas damage so that more intelligent corrective steps can be made. Analogue systems are often useful for the latter objective and in this case alloys containing Li are suitable in view of the reaction Li6 + n - He4 + He 4. Both products are gases and no serious radiation problem is produced to complicate post irradiation handling. Considerable caution is, of course, necessary in any operations in which tritium release is possible. The present program was initiated to provide a detailed study of the effects of He + H3 generated by irradiation in Li-bearing alloys. The results on Mg-Li solid solution alloys have been reported elsewhere.' This paper presents information on irradiation of an A1-0.4 pct Li alloy in which the lithium was present as highly enriched Li6 in order to maximize the radiation burnup. PROCEDURE The original intent in the selection of the alloy content was to have Li in solid solution at all temperatures. It became apparent, however, that the solubility of Li in A1 was substantially lower than that reported in the original reference consulted.' This was substantiated by the work of Nowak3 who reported solubility of less than 0.01 pct Li at 100°C. The alloy used (0.4 pct Li) was therefore two phase at room temperature. The irradiation temperature was estimated to be about 270° C, and at that temperature all or almost all of the Li would be soluble under equilibrium conditions. The precise state of the alloy under irradiation is not known. Aluminum used was 99.996 pct purity (max. impurities Si 0.002 pct, Mg 0.001 pct, Fe 0.0005 pct, and Cu 0.0005 pct). The lithium was obtained from Oak Ridge National Laboratory; 96.1 + 0.1 pct of the lithium was ~i~, but chemical impurities were 0.25 pct Ca, 0.05 pct Fe, 0.02 pct Na, 0.02 pct Cu, 0.01 pct Sr, and 0.01 pct Ba. The two metals were melted in an alumina crucible in a resistance heated furnace in an atmosphere of helium. A l-in. ingot was cast in an iron mold, machined to %-in. round, hot swaged (350°C) to 0.080-in. round, cold swaged to 0.060-in. round, and finally cold drawn to 0.040-in. round. Four-inch wire lengths were then cut and annealed at 250°C for 4 hr in helium. Irradiations were carried out in a VT hole in the Argonne CP-5 reactor. The wires were held in an aluminum jig, sixteen wires per capsule, and were maintained in a helium atmosphere for maximum heat transfer. Eight wires of pure aluminum and eight of Al-Li alloy were placed in each capsule. Argome Laboratory statements were accepted as establishing flux and exposure levels. These were based on previous experience and flux map-

Jan 1, 1961

By M. H. Cullender

THE determination of the flow characteristics of gas wells depends upon the analysis of pressure data obtained under shut-in conditions and under one or more known flow conditions. These data are commonly referred to as back-pres-sure test data, and I know you are all familiar with the back-pressure equation where, Q rate of flow, Mcfd @ standard conditions C coefficient of the back-pres-sure curve P 1 formation pressure, psia P • sand face flowing pressure, psia P2 (psia)2/1000 n exponent of the back-pres-sure curve Figure 1 is a graphical presentation of the back-pressure equation; the coefficient is the rate of flow at a difference in squared pressures of 1, in this case 2250 Mcfd, and the exponent defines the manner in which the rate of flow changes with a change in the difference in squared pressures. In Figure 1, the exponent of the back-pressure curve is 0.554 which means that for a 10-fold change in the difference in squared pressures, there will be a 3.58-fold (10 raised to the 0.554 power) change in the rate of flow.

Jan 1, 1961

By R. W. Baldwin

On page 309, column 1, the second equation should read: Ma-M1 = dlog_Pa M2-M1 d log P2

Jan 1, 1961

By R. Taggart, G. R. Purdy

DURING a study of the tempering of ß-quenched alloys of cobalt in titanium, parallel lines were observed crossing certain faces of retained-ß crystals in the early stages of tempering, Fig. 1. The lines closely resemble stress-induced martensite' or substructures attributed to clusters of faults in titanium-nickel2 and copper-silicon3 alloys. The markings were observed only in intensely etched quenched and tempered alloys having compositions ranging from 4.5 pct* Co (the composi- formed by the lines was reproduced upon repolishing and reetching. Close metallographic examination indicated that the markings were troughs, Fig. 2, and that the characteristic surface substructure persisted within the troughs. The occurrence of the troughs was associated with the age hardening reaction due to the metastable u) phase (previously reported in titanium-cobalt alloys by Raub and Beeskow4 and indicated in this work by the broadening of 0 diffraction peaks and by hardnesses approaching 600 Dph). The troughs

Jan 1, 1961

By C. E. Birchenall, R. H. Condit, M. J. Brabers

In the oxidation of pure iron above 700°C the overall rate is determined mainly by the rapid growth of wiistite, through which iron ions can diffuse rapidly.' Nickel added to the iron progressively decreases the stable range of composition of wustite.' When enough nickel is added to eliminate wiistite as a stable phase, the spinel is the fast growing phase. This investigation was undertaken to test the hypothesis that nickel substituting for iron in magnetite might decrease the rate of spinel growth by reducing the iron mobility. Nickel ferrite boules grown by the flame fusion process were purchased from the Linde Co. Chemical analysis gave an atomic ratio of iron to nickel of 2.88 and showed no other cations. They were cut into discs and ground to give flat, parallel faces. The experimental procedure employed was like that of Eisen and Birchenall in which the distribution of radioactivity diffused in from a vapor deposited surface layer was determined by counting the residual activity through a series of ground faces. The diffusivities were calculated in a manner consistent with the requirements discussed by Condit and BirchenallP The details will be given in connection with a more extensive spinel diffusion study now in progress. The results of the measurements are shown in the figure in comparison with earlier data on magnetite1 and zinc ferrite. The uncertainties arising from scatter in the activity vs distance relationship and uncertainties in the temperatures are shown by flags. Despite the scatter it is clear that substitution of a considerable part of the iron in magnetite by nickel, in this case about one third decreases the iron mobility substantially. sachs' determination of the distribution of iron and nickel in scales on iron-nickel alloys appears to show that nickel is less mobile than iron in the spinel layer. It is evident, therefore, that nickel plays several roles in reducing the oxidation rate of iron-nickel alloys. 1) It reduces progressively the stability range of wiistite. ' 2) It reduces progressively the stability range of the iron-nickel spinel phase in terms of the variation in cation to anion ratio.' 3) As shown in this investigation, it reduces the cation mobility in the spinel phase which is the faster growing phase in the absence of wiistite. The fe was obtained from the Oak Ridge National Laboratory. The research was supported by the Air Force Office of Scientific Research (ARDC) under contract number AF 18(600)-967.

Jan 1, 1961

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By Regis M. N. Pelloux, N. J. Grant

Five or six alloys each in the systems Ni-C.v, Ni-Mo, and NL-W, spaced to cover the single phase areas as well as a part of the adjacent two-phase field, were prepared as uacuum-melted alloys. Tensile tests at room temperature and stress rupture tests at 1200° and 1500°F we.ve run for time periods to give fracture in 0.1 to 500 hr. Observations mere made of solid-solution and second-phase strengthening or uleakening, coupled with studies of ductility and the role of structure on the noted behavior patterns. THE development of stable creep-resistant alloys while broad and systematic is also highly empirical. A number of simple rules have been suggestedL-" but these are based on scant data. Whereas rules for low-temperature alloy strengthening can be applied with some success in more simple systems, the extension to behavior at high temperatures (greater than about 0.4 of the absolute melting temperature) is very poorly understood and has encountered important exceptions and deviations in terms of atom size or valency effects. In particular, the occurrence of both solid-solution weakening4,5 and second-phase weakening2 at high temperatures is of interest. MATERIALS AND PROCEDURE Nickel was chosen as the base material because of its important role in current high-temperature alloy applications, because of its freedom from a phase transformation, and because of wide solubilities for many elements of interest. The selected alloys were single- and two-phase structures in the Ni-Cr,6 Ni-Mo,7 and Ni-w 8 systems. The alloys were vacuum melted and cast, utilizing high-purity raw materials, in the form of 15 lb ingots. They were readily forged into 1/2-in. bar stock (except the two highest chromium alloys). The alloy compositions are shown in Table I. Typical impurity values are: Carbon: Max 0.03 pct (except for 30 and 35 pct Cr alloys which had 0.07) Nitrogen: Max 0.005 pct (except for two of the Cr alloys which had 0.05) Sulfur: Max 0.004 pct Silicon: Max 0.05 pct Each alloy was solution treated (air quenched) to produce comparable grain size. The two-phase alloys were then overaged in an effort to produce a stable structure for testing at 1200° and 1500°F, The results are summarized in Table 11. Following the heat treatments outlined in Table 11, the bars were machined to a gage section of 1.25-in. long by 0.250-in. diam. In addition to room-temperature tensile tests, stress-rupture tests were run at 1200" and 1500°F for time periods from 0.1 to about 500 hr. RESULTS Room-Temperature Mechanical Properties—The ultimate tensile strength, total elongation, and reduction of area values for all the alloys are plotted vs atomic percent of the solute element in Fig. 1. It can be seen that for the same amount of solute element the ultimate tensile strength increases in the order chromium, molybdenum, tungsten. Elongation increases (reduction of area decreases) with increasing amounts of solute for all the solid solution alloys, the values ranging from 50 to 70 pct. The ultimate tensile strength values for the two-

Jan 1, 1961

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,' and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,' the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,' who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

[NUMERICAL CODE TO MAPS (Region Listed in Roman Numerals after Each Petroleum Section) 1 Alaska 2 Arizona 3 Black Hills 4 Boston 5 Carlsbad Potash 6 Central Appalachia 7 Chicago 8 Cleveland 9 Colorado 10 Columbia 11 Connecticut 12 Delta (VIII) 13 Detroit 14 East Texas (VI) 15 El Paso 16 Gulf Coast (VII) 17 Kansas (IX) 18 Lehigh Volley 19 Mid-Continent (IX) 20 Minnesota 21 Montana 22 Nevada 23 New York]

Jan 1, 1961

By J. S. Kirkaldy, W. J. Slater, G. R. Mason

Activation analysis for copper and manganese in 10 mg samples machined from aluminum-base diffusion couples has been used in the study of ternary diffusion in the Al-Cu-Mn system. The accuracy, economy and convenience of the method are considered to be very competitive with other methods for analysis of such small samples. Neutron-activated aluminum-zinc alloys in the range from 10 per cent to 100 per cent zinc have been equilibrated with a known volume and the vapors subsequently condensed and collected. The vapor pressures relative to pure zinc (the thermodynamic activities) have been determined at 550°C' by recording the relative count of /'-rays from zn65 in the collected samples. The method is a sensitive one, although subject to serious obstacles to experimental accuracy.

Jan 1, 1961

A general outline of the significant features in the quality and manufacture of the more common refractories is given. Where possible, linkage between quality development and control and service applicationhas been shown and explained. INTRODUCTIONThe refractory industry is no stranger to change. New processes and revision of old processes in other industries are the harbinger of new and revised products in refractories.Few of the changes are dramatic; generally they are evolutionary rather than revolutionary. New developments are additional to, and inclusive of, established practice.Therefore in this paper it is necessary to repeat much of what is already known in order to show the development taking place.FIRECLAY REFRACTORIESGeneral technology Fireclay refractories are the most common, the most varied and the most versatile of all refractories. Virtually any composition of silica and alumina up to the composition of kaolin is possible. For purposes of comparison they may be classified in the Continental fashion in accordance with chemical composition or in the American way according to "duty". That the two methods are equivalent is shown by an inspection of the alumina-silica diagram of Bbwen and Greig (1924). 'Fireclay refractories are composed of a glassy and a crystalline component derived from the chemical and physical nature of the raw materials used in their manufacture.

Jan 1, 1961

By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,' which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.' In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:' initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini's experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini's sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961

By H. Tabachnick, N. Hedley

The extraction of gold and silver from ores with alkaline cyanide solutions is well known. Cyanide solutions are also good solvents for many base metal minerals, particularly most of the copper minerals. Leaver and Woolf,1 who determined the solubilities of copper minerals in 0.10 pct sodium cyanide solution, showed that malachite, cuprite, chalcocite, and bornite are readily soluble in cyanide; least soluble are chalcopyrite and chrysocolla. The Mining Chemicals Laboratory of American Cyanamid Co. has studied the possibilities of using cyanide solutions for leaching base metals. In this article the authors present the results of their experiments with cyanide leaching to reduce the copper content of a zinc concentrate from 0.050 pct to the desired specification of less than 0.02 pct. Zinc Ore Sample: The sample of commercial zinc ore used in this investigation to produce zinc concentrates was ball mill feed ranging from 1/2 in. to fines. The ore was crushed to —10 mesh and riffled into 600-g charges for zinc flotation. Analysis revealed 4.54 pct Zn and 0.005 pct Cu. Examined microscopically, the ore consisted essentially of cream-colored sphalerite and carbonate gangue. It contained a small amount of pyrite, partly tarnished. The only copper mineral identified was chalcopyrite, mostly smaller than 20µ, some of which occurred as attachments on sphalerite. Flotation Procedure: Batches of zinc concentrates were made as required according to the following general procedure. A 600-g charge of —10 mesh ore was ground for 4 min at 60 pct solids in a laboratory steel rod mill. Screen sizing showed it to be all —35 mesh with 42 pct —200 mesh. The pulp was transferred to a Fagergren laboratory flotation machine, diluted to 25 pct solids and conditioned for 5 min with 0.6 lb per ton CuSO4, . -5H2O. It was then conditioned with 0.10 lb per ton Sodium Aerofloat promoter and floated for 5 min with pine oil as frother and creosote as froth stiff-ener. The pH during flotation was 8.5. A typical analysis of zinc concentrate subjected to leaching is 44.41 pct Zn and 0.051 pct Cu. The ratio of concentration was close to 10 to 1. Leaching Procedure: Aero Brand cyanide, technical calcium cyanide analyzing 49.5 pet NaCN equivalent, was used for all cyanide leaching tests. For each test three rougher concentrates floated as described were combined (total weight close to 180 g) and the water content adjusted to 150 ml. The percent solids in the pulp was thus 55. After a weighed amount of cyanide flakes had been added, the pulp was agitated on rolls for a given period, then filtered and washed. Filtrate and washed concentrate were assayed for copper content. The procedure for ammonia leaching was similar to the cyanide process. A series of tests was run in which the effects of ammonia as a solvent for copper in the zinc rougher concentrate were investigated. In each test 180 g of zinc rougher concentrate was leached with 150 ml of ammonia solution. Various strengths of ammonia and times of leaching were investigated. The results are shown in Table I. It is apparent that ammonia was a poor solvent for copper in the zinc concentrate; 60 min of agitation with a relatively strong NH:, solution extracted only 2 pct of the copper. CYANIDE LEACHING TESTS Effect of Solution Strength: The solvent effects of 0.125, 0.187, and 0.250 pct NaCN equivalent solutions were compared for leaching periods of 15 min. Residue and filtrate were assayed for copper content. The copper content of the filtrate plus wash was calculated back to the original volume of cyanide solution (150 ml). The effects of cyanide strength are given in Table II, It will be noted that 15 min leaching with 0.25 pct NaCN equivalent solution extracted 74.6 pct of the copper in the zinc concentrate. The leached product assayed 0.013 pct Cu, appreciably below the required specification of 0.020 pct. Effect of Leaching Time: Portions of zinc concentrate were leached with 0.25 pct NaCN equivalent

Jan 1, 1961

By N. F. Mott

Jan 1, 1961

By J. D. Corbett

The spatial coincidence of the seven anomalies is obvious, even though the self-potential is offset northward. Because the ratio, as an indicator of conductivity, is a relative estimate at best, concise interpretation is limited in almost every instance to the location of a conductor or conductor axis. When related to the initial phase of an exploration program, magnitudes and ratios similar to those obtained from any one of the methods described, would be sufficiently attractive to warrant further investigation. The compilation shown is an empirical comparison of actual field results and no emphasis has intentionally been placed on the relative merits of one method in respect to another. Too many additional factors, i.e., size, depth and conductivity of overburden, etc., that cannot unequivocally be answered, enter into such a comparison before a relative evaluation can be made.

Jan 1, 1961

By C. B. Sclar and

A graphical solution is presented for the equation v =v &-cU where vb is the volume of liquid b of density 6 that must be added to liquid a of volume va and density d, in order to obtain a heavy-liquid solution of preferred density dm for mineral fractionation. The equation is valid only for pairs of liquids whose volumes are additive, but empirical density-composi-tion data show that this condition is met over wide compositional ranges by all of the heavy solutions that are commonly used for mineralogical analysis. The chart is a nomograph which consists of two horizontal volume scales ad a vertical density scale arranged so that one volume scale occurs on each side of the density scale. All the scales are linear. For two liquids of density d, and &, respectively, each volume scale has an independent level on the density scale, ad the graphical solution for vb on the nomograph is obtained by construction of one straight line. The chart can be prepared easily to cover any density range with any desired accuracy by proper selection of the scales. Heavy-liquid separation of particulate samples is an indispensable analytical procedure in the mineralogical and mineral-process ing laboratory. Heavy liquids may be used 1) to isolate specific minerals in the form of high purity products or to fractionate samples into several products with density limits for petrographic, chemical, spectrographic, and X-ray diffraction analysis,'-' 2) to determine the density of minerals,'-l4 3) to facilitate the recognition and identification of optically similar associated minerals,15 and 4) to determine quantitatively the degree of liberation of ore minerals in ores and mill products at various limiting sizes." The preparation and recovery of heavy liquids suitable for mineralogical analysis are discussed fully in the literature and operational procedures and special equipment for heavy-liquid separation are described in numerous references.'747837' 13,18,25-42 Useful tabulations of heavy liquids for mineralogical analysis are given by Tickell, Mil-ner,' Twenhofel and Tyler,' and Lange and a very complete up-to-date list of minerals arranged according to increasing density is given by Mursky and Thompson. USEFULNESS OF THE DENSITY CHART For any particulate sample, the limiting densities selected for its fractionation by means of heavy- liquid separation depend on the respective densities of the constituent minerals and the specific objectives of the separation. In many instances, the densities of readily available and practicable heavy liquids do not coincide with those that are required, and suitable liquids of the proper density are obtained by dilution with miscible liquids. In the general case, one may wish to mix either a pure liquid (A) or a solution of two miscible liquids (AP,,) of known density with either a pure liquid (B) or a different solution of the two miscible liquids (A,B,) of higher or lower density in order to obtain a final liquid of the preferred density. In conventional practice, the latter is reached empirically by trial-and-error addition of increments of one liquid to the other. The density of the final solution may be determined either by accurately weighing a known volume of the final liquid,'' 532;4;40, or by means of I)a Westphal balance, 2)a hydrometer, a refractometer in the case of binary liquid systems for which density-refractive index data are available,15 4) natural or synthetic .indicators of known density, a pycno-meter. Like all trial-and-error methods, these procedures are time consuming and many require special equipment which may not be available, The purpose of this paper is to show that the volume of a liquid of known density which is to be added to another liquid of known volume and density in order to obtain a solution with an intermediate preferred density may be determined rapidly and accurately by a graphical method provided that the two liquids form ideal or quasi-ideal solutions whose volumes are additive. Empirical data47'8~'8~4B'49 show that solutions prepared from pairs of miscible

Jan 1, 1961

By D W. MacFadgen

THE operating advantages of the longwall retreating system of mining, as opposed to longwall advancing, have been well known for many years. Although retreat walls have been successfully worked in the past in some of the collieries of the Dominion Steel and Coal Corporation in the Sydney, Picton and Cumberland areas, the adoption of longwaIl retreating as the general sys-tem of mining has not been attractive in the Sydney field, due to the time and expenditures required to drive roadways to the boundary. In addition. difficulties in maintaining effective ventilation on the faces, especially under conditions of low barometer, have made the operators in the field hesitant to adopt this as the general system of mining. The development of a machine capable of rapid entry drivage has made possible the driving of the necessary road ways to the boundary at a moderate cost, completely changing the picture and making a retreat system more attractive.

Jan 1, 1961